CN106468857B - Photosensitive resin composition and application thereof - Google Patents

Photosensitive resin composition and application thereof Download PDF

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CN106468857B
CN106468857B CN201610635329.4A CN201610635329A CN106468857B CN 106468857 B CN106468857 B CN 106468857B CN 201610635329 A CN201610635329 A CN 201610635329A CN 106468857 B CN106468857 B CN 106468857B
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methyl
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CN106468857A (en
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蔡宇杰
陈奕光
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Chi Mei Corp
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G03F7/0751—Silicon-containing compounds used as adhesion-promoting additives or as means to improve adhesion
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G03F7/0754—Non-macromolecular compounds containing silicon-to-silicon bonds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G03F7/0755—Non-macromolecular compounds containing Si-O, Si-C or Si-N bonds
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/133357—Planarisation layers

Abstract

A photosensitive resin composition comprising an alkali-soluble resin (A), a compound (B) having an ethylenically unsaturated group, a photoinitiator (C), a solvent (D), and a silane compound (E), wherein the silane compound (E) comprises a silane compound (E-1) represented by the formula (I):

Description

Photosensitive polymer combination and its application
Technical field
The invention relates to a kind of photosensitive polymer combination and its applications, and a kind of especially above-mentioned photonasty of use Resin be formed by with good refractive index and with the film of molybdenum adherence and its application.
Background technique
It is important technology in forming protective film on substrate in the field of manufacture liquid crystal display element.When manufacture such as liquid When the optical elements such as crystal display element or solid state image pickup device, processing routine need to be carried out under critical conditions, such as in substrate table Face is impregnated with acid solution or alkaline solution, or high with generated part when sputter (Sputtering) formation wiring electrode layer Temperature.Therefore, it need to be laid with protective film on the surface of these elements, damaging components when preventing manufacture.Now, the protective film is usual All with photosensitive polymer combination it is coated, exposure, development etc. processing procedures and be formed on substrate.
The characteristic for resisting above-mentioned critical conditions processing to have protective film, protective film, which removes, need to have the high grade of transparency, surface Outside the fundamental characteristics of hardness and flatness, also need that there is excellent adhesive force between substrate.Importantly, protective film needs to have There are the characteristics such as good water resistance, solvent resistance, acid resistance, alkali resistance.In afore-mentioned characteristics, since protective film is formed at coloured silk On colo(u)r filter or substrate, the requirement to transparency is high, first when being applied to liquid crystal display if the transparency of protective film is bad When part, the luminance shortage of liquid crystal display element will be caused, and influences the display quality of liquid crystal display element.
For the transparency for improving protective film, Japanese Patent Laid-Open 2010-054561 is disclosed a kind of the photosensitive of protective film Composition, it includes alkali-soluble binding resin (A), the compound (B) of ethylene unsaturated group, light initiator (C) and solvents (D).Wherein the combination equivalent of unsaturated bond is and the ethylene between 90 to 450g/eq in the compound (B) of ethylene unsaturated group Property unsaturated group compound (B) in, the unsaturated double-bond of single compound is between 2 to 4 and alkali-soluble bonding The weight average molecular weight of resin (A) is between 10,000 to 20,000.
On the other hand, No. 2004-240241 announcement photosensitive composition of Japanese Patent Laid-Open, it includes co-polymers (A), second The polymer (B) and light initiator (C) of the unsaturated base of alkene.Wherein co-polymer (A) be by the unsaturated carboxylic acid of ethylene (acid anhydride), Have compound institute's combined polymerization of the compound and the unsaturated base of other ethylene of the unsaturated base of ethylene of epoxy group and obtains.Light rises Beginning agent (C) is 2- diacetyl-[4- methylthio phenyl] -2- (O- oxime acetate salt), 1,2- diacetyl -1- (4- morpholino phenyl) -2- (O- benzoyl oxime), 1,2- octadione- 1- [4- thiophenyl benzene] -2- [O- (4- toluyl) oxime] or its analog.However, The photosensitive polymer combination be formed by film be unable to satisfy the refractive index of industry pair now and with molybdenum adherence increasingly Raised demand.
Therefore, how to reach current industry refractive index and the requirement with molybdenum adherence simultaneously, for belonging to the present invention Make great efforts the target of research in technical field.
Summary of the invention
One of the objects of the present invention is to provide a kind of photosensitive polymer combination, with take into account current industry refractive index and With the requirement of molybdenum adherence.
Therefore, one aspect of the present invention is to provide a kind of photosensitive polymer combination.
It is made using above-mentioned photosensitive polymer combination it is another aspect of the invention to provide a kind of film , and its with good refractive index and with molybdenum adherence.
Another aspect of the present invention is to provide a kind of element, is comprising above-mentioned film.
Above-mentioned aspect according to the present invention proposes a kind of photosensitive polymer combination, be comprising alkali soluble resin (A), Compound (B), light initiator (C), solvent (D) and silane compound (E) with ethylene unsaturated group, wherein silanization Closing object (E) includes silane compound (E-1), and analysis states it individually below.
Photosensitive polymer combination
Alkali soluble resin (A)
Resin (A-1) with unsaturated group
Alkali soluble resin (A) includes the resin (A-1) with unsaturated group, this resin (A-1) with unsaturated group It is to be carried out obtained by polymerization reaction as a mixture, and this mixture includes the epoxide at least two epoxy groups And the compound (a-1-2) at least one carboxylic acid group Yu at least one ethylene unsaturated group (a-1-1),.Except this it Outside, it includes compound carboxylic acid anhydride (a-1-3) and/or the compound (a-1-4) containing epoxy group that mixture above-mentioned is more alternative.
In a specific example of the present invention, this has at least two epoxy groups of having of the resin (A-1) of unsaturated group Epoxide (a-1-1) has the structure as shown in following formula (a-I):
Figure BDA0001070387350000031
In formula (a-I), R1、R2、R3And R4It is respectively independent to indicate hydrogen atom, halogen atom, the alkane that carbon number is 1 to 5 The aralkyl that the aromatic radical or carbon number that alkoxy that base, carbon number are 1 to 5, carbon number are 6 to 12 are 6 to 12.
The epoxide (a-1-1) at least two epoxy groups of previously described formula (a-I) may include but be not limited to by double Phenol fluorenes type compound (bisphenol fluorene) contains epoxy obtained by reacting with halogenated epoxy propane (epihalohydrin) The bisphenol fluorene type compound of base.
Profess it, above-mentioned bisphenol fluorene type compound it is specific for example: 9,9- bis- (4- hydroxy phenyl) fluorenes [9,9-bis (4- Hydroxyphenyl) fluorene], bis- (the 4- hydroxy-3-methyl phenyl) fluorenes [9,9-bis (4-hydroxy-3- of 9,9- Methylphenyl) fluorene], bis- (4- hydroxyl -3- chlorphenyl) fluorenes [9,9-bis (4-hydroxy-3- of 9,9- Chlorophenyl) fluorene], bis- (4- hydroxyl -3- bromophenyl) fluorenes [9,9-bis (4-hydroxy-3- of 9,9- Bromophenyl) fluorene], bis- (4- hydroxyl -3- fluorophenyl) fluorenes [9,9-bis (4-hydroxy-3- of 9,9- Fluorophenyl) fluorene], bis- (the 4- hydroxy 3-methoxybenzene base) fluorenes [9,9-bis (4-hydroxy-3- of 9,9- Methoxyphenyl) fluorene], bis- (4- hydroxyl -3,5- 3,5-dimethylphenyl) fluorenes of 9,9- [9,9-bis (4-hydroxy-3, 5-dimethylphenyl) fluorene], bis- (4- hydroxyl -3,5- dichlorophenyl) fluorenes of 9,9- [9,9-bis (4-hydroxy-3, 5-dichlorophenyl) fluorene], bis- (4- hydroxyl -3,5- dibromo phenyl) fluorenes of 9,9- [9,9-bis (4-hydroxy-3, 5-dibromophenyl) fluorene] etc. compounds.
Above-mentioned suitable halogenated epoxy propane (epihalohydrin) may include but be not limited to epichlorohydrin (epichlorohydrin) or the bromo- 1,2 epoxy prapane of 3- (epibromohydrin) etc..
The quotient that the above-mentioned resulting bisphenol fluorene type compound containing epoxy group is manufactured including but not limited to (1) Nippon Steel's chemistry Product: such as ESF-300；(2) commodity of Osaka gas manufacture: such as PG-100, EG-210；(3)S.M.S The commodity of Technology Co. manufacture: such as SMS-F9PhPG, SMS-F9CrG, SMS-F914PG.
In another concrete example of the invention, the resin (A-1) with unsaturated group has at least two epoxy groups Epoxide (a-1-1) has the structure as shown in following formula (a-II):
Figure BDA0001070387350000041
In formula (a-II), R5To R18It is respectively independent to indicate hydrogen atom, halogen atom, the alkyl or carbon number that carbon number is 1 to 8 For 6 to 15 aromatic radical；And n indicates integer of 0 to 10.
The epoxide (a-1-1) at least two epoxy groups of previously described formula (a-II) can be for example in alkali metal hydrogen-oxygen In the presence of compound, the compound with following formula (a-II-1) structure is made to be reacted and be obtained with halogenated epoxy propane:
Figure BDA0001070387350000042
In formula (a-II-1), R5To R18And the definition of n be respectively with the R in formula (a-II)5To R18And the definition of n It is identical, it does not repeat separately herein.
Furthermore the epoxide (a-1-1) at least two epoxy groups of previously described formula (a-II) is in acid catalyst In the presence of, after carrying out condensation reaction with phenol (phenol) class using the compound with following formula (a-II-2) structure, formation has The compound of formula (a-II-1) structure.Then, excessive halogenated epoxy propane is added and carries out de-hydrogen halide (dehydrohalogenation), the epoxide (a-1- at least two epoxy groups of above-mentioned formula (a-II) is obtained 1):
Figure BDA0001070387350000043
In above formula (a-II-2), R19With R20Respectively identical or different hydrogen atom, halogen atom, carbon number are 1 to 8 Alkyl or carbon number be 6 to 15 aromatic radical；X1And X2Respectively identical or different halogen atom, the alkyl that carbon number is 1 to 6 Or the alkoxy that carbon number is 1 to 6.Preferably, halogen atom above-mentioned can such as chlorine or bromine, alkyl above-mentioned can such as methyl, Ethyl or tert-butyl, alkoxy above-mentioned can such as methoxy or ethoxies.
Above-mentioned suitable phenols it is specific for example: phenol (phenol), cresols (cresol), diethylstilbestrol (ethylphenol), n- Third phenol (n-propylphenol), isobutyl phenol (isobutylphenol), t- fourth phenol (t-butylphenol), octyl phenol (octylphenol), nonyl phenol (nonylphenol), stubble phenol (xylenol), methyl butyl phenol (methylbutylphenol), di-tert-butylphenol (di-t-butylphenol), phenol ethylene (vinylphenol), propylene benzene Phenol (propenylphenol), acetylene phenol (ethynlphenol), penta phenol of ring (cyclopentylphenol), cyclohexyl Phenol (cyclohexylphenol) or cyclohexyl cresols (cyclohexylcresol) etc..Phenols above-mentioned generally can be individually a kind of Or a variety of uses of mixing.
Usage amount based on the above-mentioned compound with formula (a-II-2) structure is 1 mole, and the usage amount of the phenols is 0.5 It is so preferable with 2 moles to 15 moles mole to 20 moles.
Acid catalyst above-mentioned it is specific for example: hydrochloric acid, sulfuric acid, p-methyl benzenesulfonic acid (p-toluenesulfonic Acid), oxalic acid (oxalic acid), boron trifluoride (boron trifluoride), anhydrous aluminum chloride (anhydrous Aluminium chloride), zinc chloride (zinc chloride) etc., be so preferable with p-methyl benzenesulfonic acid, sulfuric acid or hydrochloric acid. Acid catalyst above-mentioned can the individually a kind of or a variety of uses of mixing.
Though preferably so there is formula (a- based on above-mentioned in addition, the usage amount of acid catalyst above-mentioned is without particular limitation II-2) usage amount of the compound of structure is 100 weight percent (wt%), the usage amount of acid catalyst be 0.1wt% extremely 30wt%.
Condensation reaction above-mentioned can be solvent-free or in presence of organic solvent carry out.Secondly, above-mentioned is organic molten Agent it is specific for example: toluene (toluene), dimethylbenzene (xylene) or methyl iso-butyl ketone (MIBK) (methyl isobutyl Ketone) etc..Above-mentioned organic solvent can the individually a kind of or a variety of uses of mixing.
Total weight based on compound and phenols with formula (a-II-2) structure is 100wt%, above-mentioned organic solvent Usage amount be 50wt% to 300wt%, be so preferable with 100wt% to 250wt%.In addition, the behaviour of condensation reaction above-mentioned Making temperature is 40 DEG C to 180 DEG C, and the operating time of condensation reaction is 1 hour to 8 hours.
After completing condensation reaction above-mentioned, it can be neutralized or washing process.Neutralisation treatment above-mentioned is will be anti- The pH value of solution after answering is adjusted to pH3 to pH7, is so preferable with pH5 to pH7.Neutralizer can be used in washing process above-mentioned It carries out, wherein this neutralizer is alkaline matter, and it is specifically for example: sodium hydroxide (sodium hydroxide), hydroxide The alkali metal hydroxides such as potassium (potassium hydroxide)；Calcium hydroxide (calcium hydroxide), magnesium hydroxide Alkaline-earth metals hydroxide such as (magnesium hydroxide)；Diethylene triamine (diethylene triamine), Tetramine (triethylenetetramine), aniline (aniline), phenylenediamine (phenylene diamine) etc. three times Organic amine；And ammonia (ammonia), sodium dihydrogen phosphate (sodium dihydrogen phosphate) etc..At washing above-mentioned Prior art method progress can be used in reason, for example, the aqueous solution containing neutralizer is added, extraction is repeated in solution after the reaction ?.After neutralized processing or washing process, is handled through heating under reduced pressure, unreacted phenols and solvent are given into distillation, gone forward side by side Row concentration, can be obtained the compound with formula (a-II-1) structure.
Above-mentioned suitable halogenated epoxy propane it is specific for example: the bromo- 1,2 epoxy prapane of epichlorohydrin, 3- Or above-mentioned any combination.Before carrying out de-hydrogen halide above-mentioned, hydrogen can be added or added in reaction process in advance The alkali metal hydroxides such as sodium oxide molybdena, potassium hydroxide.The operation temperature of de-hydrogen halide above-mentioned is 20 DEG C to 120 DEG C, Operating time range is 1 hour to 10 hours.
In one embodiment, added alkali metal hydroxide also can be used its water-soluble in above-mentioned de-hydrogen halide Liquid.In this embodiment, above-mentioned alkali metal hydroxide aqueous solution is continuously added to same in de-hydrogen halide system When, it can be under decompression or normal pressure, continuous still water outlet and halogenated epoxy propane separate whereby and remove water, while can be by halogenation Propylene oxide is continuously back in reaction system.
Before above-mentioned de-hydrogen halide carries out, tetramethyl-ammonium chloride (tetramethyl ammonium can be also added Chloride), tetramethylammonium bromide (tetramethyl ammonium bromide), trimethyl benzyl ammonia chloride (trimethyl Benzyl ammonium chloride) etc. quarternary ammonium salt as catalyst, and at 50 DEG C to 150 DEG C, reaction 1 hour is extremely 5 hours, alkali metal hydroxide or its aqueous solution are added, at a temperature of 20 DEG C to 120 DEG C, reacts it 1 hour to 10 Hour, to carry out de-hydrogen halide.
It is 1 equivalent, above-mentioned halogenation based on the hydroxyl total yield in the above-mentioned compound with formula (a-II-1) structure The usage amount of propylene oxide is 1 equivalent to 20 equivalents, is so preferable with 2 equivalents to 10 equivalents.There is formula (a- based on above-mentioned II-1) the hydroxyl total yield in the compound of structure is 1 equivalent, the alkali metal hydroxide added in above-mentioned de-hydrogen halide The usage amount of object is 0.8 equivalent to 15 equivalents, is so preferable with 0.9 equivalent to 11 equivalents.
In addition, can also be added except the alcohols such as methanol, ethyl alcohol, also to go on smoothly above-mentioned de-hydrogen halide The aprotics such as dimethyl sulfone (dimethyl sulfone), dimethyl sulfoxide (dimethyl sulfoxide) can be added (aprotic) polarity solvent etc. is reacted.Using alcohols, based on the total of above-mentioned halogenated epoxy propane Amount is 100wt%, and the usage amount of alcohols is 2wt% to 20wt%.It is so preferable with 4wt% to 15wt%.Using non-proton Property polarity solvent example in, the total amount based on halogenated epoxy propane be 100wt%, the use of the polarity solvent of aprotic It is so preferable with 10wt% to 90wt% that amount, which is 5wt% to 100wt%,.
After completing de-hydrogen halide, washing process is optionally carried out.Later, in the way of heating decompression, Such as it is 110 DEG C to 250 DEG C in temperature and pressure is 1.3kPa (10mmHg) hereinafter, removing halogenated epoxy propane, alcohols and non- Polarity solvent of protic etc..
In order to avoid the epoxy resin of formation contains hydrolyzable halogen, the solution after de-hydrogen halide can be added Toluene, methyl iso-butyl ketone (MIBK) (methyl isobutyl ketone) equal solvent, and the alkali such as sodium hydroxide, potassium hydroxide gold is added Belong to hydroxide aqueous solution, carries out de-hydrogen halide again.In de-hydrogen halide, formula (a-II- is had based on above-mentioned 1) the hydroxyl total yield in the compound of structure is 1 equivalent, and the usage amount of alkali metal hydroxide is 0.01 mole to 0.3 and rubs You, is so preferable with 0.05 mole to 0.2 mole.In addition, the operating temperature range of above-mentioned de-hydrogen halide be 50 DEG C extremely 120 DEG C, and its operating time range is 0.5 hour to 2 hours.
After completing de-hydrogen halide, by filtering and washing and etc. removal salt.In addition, being depressurized using heating Mode, toluene, methyl iso-butyl ketone (MIBK) equal solvent are given into distillation, then can be obtained such as structural formula (a-II) shown in at least The epoxide (a-1-1) of two epoxy groups.Epoxide (the a- at least two epoxy groups of above-mentioned formula (a-II) It 1-1) can include but not limited to, for example, the Japanese chemical drug system such as trade name NC-3000, NC-3000H, NC-3000S and NC-3000P Commodity.
In a specific example of the present invention, there is this of the resin (A-1) of unsaturated group to have at least one carboxylic acid group for this Compound (a-1-2) at least one ethylene unsaturated group is selected from a group as composed by following (1) to (3): (1) acrylic acid, methacrylic acid, 2- methylacryoyloxyethyl succinic acid (2- Methacryloyloxyethylbutanedioic acid), 2- methacryl oxygen-butyl succinic acid, 2- methacryloxypropyl Ethyl adipic acid, 2- methacryl oxygen-butyl adipic acid, 2- methylacryoyloxyethyl hexahydrophthalic acid, 2- methyl-prop Alkene acyloxyethyl maleic acid, 2- methacryloxypropyl maleic acid, 2- methacryl oxygen-butyl maleic acid, 2- metering system Monomethacryloxypropyl succinic acid, 2- methacryloxypropyl adipic acid, 2- methacryloxypropyl tetrahydrophthalic acid, 2- first Base acryloxypropyl phthalic acid, 2- methacryl oxygen-butyl phthalic acid or 2- methacryl oxygen-butyl hydrogen Phthalic acid；(2) compound obtained by being reacted as (methyl) acrylate of hydroxyl with dicarboxylic acid compound, wherein two First carboxylic acid compound is including but not limited to adipic acid, succinic acid, maleic acid, phthalic acid；(3) by (methyl) third of hydroxyl Half ester compound obtained by olefin(e) acid ester is reacted with compound carboxylic acid anhydride, wherein (methyl) acrylate of hydroxyl include but unlimited In 2- hydroxyethylmethacry,ate [(2-hydroxyethyl) acrylate], 2- hydroxyethyl methacrylate [(2- Hydroxyethyl) methacrylate], 2- acrylate [(2-hydroxypropyl) acrylate], 2- hydroxyl Base propyl methacrylate [(2-hydroxypropyl) methacrylate], 4- hydroxybutyl acrylate [(4- Hydroxybutyl) acrylate], 4- hydroxybutyl methacrylate [(4-hydroxybutyl) methacrylate], Or pentaerythritol acrylate trimethyl etc..In addition, compound carboxylic acid anhydride described herein can be with aftermentioned with unsaturated group Compound carboxylic acid anhydride (a-1-3) contained by the mixture of resin (A-1) is identical, therefore is not repeated separately.
Really it has been observed that the mixture of the above-mentioned resin (A-1) with unsaturated group is more alternative comprising carboxylic acid anhydrides chemical combination Object (a-1-3) and/or compound (a-1-4) containing epoxy group.Compound carboxylic acid anhydride (a-1-3) above-mentioned can be selected from by following (1) to a group composed by (2): (1) succinic anhydride (butanedioic anhydride), maleic anhydride (maleic Anhydride), itaconic anhydride (itaconic anhydride), phthalic anhydride (phthalic anhydride), tetrahydro Phthalic anhydride (tetrahydrophthalic anhydride), hexahydrophthalic anhydride (hexahydrophthalic Anhydride), methyl tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl bridging methylene tetrahydro neighbour benzene two Formic anhydride (methyl endo-methylene tetrahydro phthalic anhydride), chlorendic anhydride (chlorendic anhydride), glutaric anhydride or inclined three benzoyl oxides (1,3-dioxoisobenzofuran-5- Carboxylic anhydride) etc. dicarboxylic acid anhydrides compound；And (2) benzophenone tetracarboxylic dianhydride (benzophenone tetracarboxylic dianhydride；BTDA), double pyromellitic dianhydride or double phenylate tetracarboxylic acids The quaternarys compound carboxylic acid anhydride such as dianhydride.
Compound (a-1-4) above-mentioned containing epoxy group is selected from glycidyl methacrylate, 3,4- epoxy basic ring Hexyl methacrylate, the glycidyl ether compound containing unsaturated group, the unsaturated compound containing epoxy group or above-mentioned A group composed by any combination.The aforementioned glycidyl ether compound containing unsaturated group is including but not limited to trade name Denacol EX-111、EX-121Denacol、Denacol EX-141、Denacol EX-145、Denacol EX-146、 Denacol EX-171, Denacol EX-192 etc. (the above are the commodity of Chang Lai chemical conversion industry Co., Ltd.).
The aforementioned resin (A-1) with unsaturated group can be by the epoxy compound at least two epoxy groups of formula (a-I) Object (a-1-1) polymerize with the compound (a-1-2) at least one carboxylic acid group and at least one ethylene unsaturated group Reaction forms the reaction product of a hydroxyl, then, then adds obtained by compound carboxylic acid anhydride (a-1-3) reacted.Preferably Ground, the hydroxyl total yield of the reaction product based on hydroxyl above-mentioned are 1 equivalent, contained by compound carboxylic acid anhydride (a-1-3) The equivalent of anhydride group is 0.4 equivalent to 1 equivalent, is so preferable with 0.75 equivalent to 1 equivalent.As the multiple compound carboxylic acid anhydrides of use (a-1-3) when, it can sequentially add in reaction or add simultaneously.Preferably, compound carboxylic acid anhydride (a-1-3) is using binary carboxylic Anhydride compound and when quaternary compound carboxylic acid anhydride, the molar ratio of dicarboxylic acid anhydride compound and quaternary compound carboxylic acid anhydride are 1/99 to 90/10, it is so preferable with 5/95 to 80/20.In addition, the operating temperature range of above-mentioned reaction is 50 DEG C to 130 DEG C.
The aforementioned resin (A-1) with unsaturated group can be by the epoxy at least two epoxy groups of structural formula (a-II) Compound (a-1-1) is carried out with the compound (a-1-2) at least one carboxylic acid group and at least one ethylene unsaturated group Reaction forms the reaction product of a hydroxyl, then, then adds compound carboxylic acid anhydride (a-1-3) and/or the chemical combination containing epoxy group Object (a-1-4) carries out obtained by polymerization reaction.Preferably, being based on the epoxy compound at least two epoxy groups of formula (a-II) Epoxy group total yield on object (a-1-1) is 1 equivalent, above-mentioned to have at least one carboxylic acid group and at least one ethylene insatiable hunger Acid value equivalent with the compound (a-1-2) of base is 0.8 equivalent to 1.5 equivalents, is so preferable with 0.9 equivalent to 1.1 equivalents.Base In hydroxyl above-mentioned reaction product hydroxyl total amount be 100 molar percentages (mole %), compound carboxylic acid anhydride (a-1-3) Usage amount be 10 moles of % to 100 moles of %, be so preferable with 20 moles of % to 100 moles of %, and with 30 moles of % to 100 Mole % is more preferably.
When preparing resin (A-1) above-mentioned with unsaturated group, to accelerate reaction, it will usually add in reaction solution Add alkali compounds as catalysts.Catalysts above-mentioned can be used alone or as a mixture, and catalytic reaction above-mentioned Agent is including but not limited to triphenylphosphine (triphenyl phosphine), antimony triphenyl (triphenyl stibine), three second Amine (triethylamine), triethanolamine (triethanolamine), tetramethyl ammonium chloride (tetramethylammonium Chloride), benzyltriethylammonium chloride (benzyltriethylammonium chloride) etc..Preferably, based on aforementioned Epoxide (a-1-1) at least two epoxy groups with there is at least one carboxylic acid group and at least one ethylene not The total weight for being saturated the compound (a-1-2) of base is 100 parts by weight, and the usage amount of catalysts is 0.01 parts by weight to 10 weights Part is measured, is so preferable with 0.3 parts by weight to 5 parts by weight.
In addition, usually can also add polymerization inhibitor in reaction solution to control the degree of polymerization.Above-mentioned polymerization inhibitor may include But it is not limited to methoxyl group phenol (methoxyphenol), methylnaphthohydroquinone (methylhydroquinone), quinhydrones (hydroquinone), DBPC 2,6 ditertiary butyl p cresol (2,6-di-t-butyl-p-cresol) or phenthazine (phenothiazine) etc..Above-mentioned polymerization inhibitor generally can the individually a kind of or a variety of uses of mixing.Had at least based on above-mentioned The epoxide (a-1-1) of two epoxy groups and the change at least one carboxylic acid group and at least one ethylene unsaturated group The total weight for closing object (a-1-2) is 100 parts by weight, and the usage amount of polymerization inhibitor is 0.01 parts by weight to 10 parts by weight, so with 0.1 weight It is preferable for measuring part to 5 parts by weight.
When preparing resin (A-1) with unsaturated group, polymerization solvent can be used when necessary.Polymerization above-mentioned Reaction dissolvent it is specific for example: the alcohols chemical combination such as ethyl alcohol, propyl alcohol, isopropanol, butanol, isobutanol, 2- butanol, hexanol or ethylene glycol Object；The ketone compounds such as methyl ethyl ketone or cyclohexanone；The aromatic hydrocarbon compound such as toluene or dimethylbenzene；It matches Luo element or butyl matches Luo Plain (cellosolve) the class compound of the match such as plain (butyl cellosolve) Luo；Card must appropriate (carbitol) or butyl card must be appropriate Equal cards must appropriate class compound；The propylene glycol alkyls ether compound such as propylene glycol monomethyl ether；Dipropylene glycol monomethyl ether [di (propylene glycol) methyl ether] etc. more propylene glycol alkyl ethers [poly (propylene glycol) alkyl Ether] class compound；Ethyl acetate, butyl acetate, ethylene glycol ether acetate (ethylene glycol monoethyl Ether acetate) or the acetic acid such as propylene glycol methyl ether acetate (propylene glycol methyl ether acetate) Ester type compound；Lactic acid alkyl ester (the alkyl such as ethyl lactate (ethyl lactate) or butyl lactate (butyl lactate) Lactate) class compound；Or dialkyl group glycol ethers.Polymerization solvent above-mentioned generally can be individually a kind of or be mixed a variety of It uses.In addition, the acid value of the resin (A-1) above-mentioned with unsaturated group be 50mgKOH/g to 200mgKOH/g, so with 60mgKOH/g to 150mgKOH/g is preferable.
The weight average molecular weight of alkali soluble resin (A-1) of the invention is generally 1,200 to 15,000, preferably 1, 500 to 13,000, more preferably 1,800 to 10,000.
Usage amount based on alkali soluble resin (A) is 100 parts by weight, the aforementioned resin (A-1) with unsaturated group Usage amount is 30 parts by weight to 100 parts by weight, is so preferable with 50 parts by weight to 100 parts by weight, and with 70 parts by weight to 100 weights Measuring part is more preferably.If the refraction of resulting Photosensitve resin composition can be improved when using resin (A-1) with unsaturated group Rate.
Though it is reluctant to be limited by theory, it is believed that because refractive index and molecular polarizability are directly proportional, and aromatic rings belongs to high pole Rate molecular configuration, therefore, the resin (A-1) with unsaturated group have aromatic ring structure, therefore refractive index can be improved.
Alkali soluble resin (A-2)
Alkali soluble resin (A) according to the present invention preferably additionally comprises alkali soluble resin (A-2).
" (methyl) acrylic acid " used herein word indicates acrylic acid and/or methacrylic acid；" (methyl) propylene An acyl group " word indicates acryloyl group and/or methylacryloyl；" (methyl) acrylate " word indicate acrylate and/or Methacrylate.
The alkali soluble resin (A-2) according to the present invention refers to the resin dissolved in alkaline aqueous solution, and construction is simultaneously It is not particularly limited, in a preferred embodiment of the invention, which refers to resin, benzene containing carboxylic acid group Phenol-novolaks (phenol-novolac) resin etc., more preferably, the alkali soluble resin (A-2) be by unsaturated carboxylic acid or Unsaturated carboxylic acid anhydrides compound (a1), the unsaturated compound (a2) containing epoxy group and/or other unsaturated compounds (a3) exist In the presence of polymerization initiators appropriate in solvent institute's combined polymerization and obtain.
When alkali soluble resin (A-2) is by unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides compound (a1), containing epoxy group Unsaturated compound (a2) and/or other unsaturated compounds (a3) institute's combined polymerization and when, be based on alkali soluble resin (A-2) Polymerization with the usage amount of compound be 100 parts by weight, unsaturated carboxylic acid of the invention or unsaturated carboxylic acid anhydrides compound (a1) Usage amount be 5 to 50 parts by weight, preferably 8 to 45 parts by weight, more preferably 10 to 40 parts by weight.Unsaturated carboxylic acid or unsaturation Compound carboxylic acid anhydride (a1) refers to the compound of the unsaturated bond combined comprising carboxylic acid group or carboxylic anhydride structure and polymerization, knot There is no particular restriction for structure, such as unsaturated monocarboxylic compound, unsaturated dicarboxylic compound, unsaturated acid anhydride compound, more Ring-like unsaturated carboxylic acid compounds, polycyclic type unsaturated dicarboxylic compound, polycyclic type unsaturated acid anhydride compound.
In concrete example of the invention, unsaturated monocarboxylic compound is (methyl) acrylic acid, butenoic acid, α-chloropropene Acid, ethylacrylic acid, cinnamic acid, 2- (methyl) acryloyloxyethyl succinate, 2- (methyl) acryloyloxyethyl hexahydro Phthalic acid ester, 2- (methyl) acryloyloxyethyl phthalic acid ester, omega- carboxy-polycaprolactone polyalcohol mono acrylic ester (trade name ARONIX M-5300, East Asia synthesis system).
In concrete example of the invention, unsaturated dicarboxylic compound is maleic acid, fumaric acid, mesaconic acid, clothing health Acid, citraconic acid etc..In concrete example of the invention, unsaturated dicarboxylic acid anhydride compound is aforementioned unsaturated dicarboxylic compound Anhydride compound.
In concrete example of the invention, polycyclic type unsaturated carboxylic acid compounds be bicyclic [2.2.1] hept-2-ene" of 5- carboxyl, 5- carboxyl -5- methyl bicycle [2.2.1] hept-2-ene", bicyclic [2.2.1] hept-2-ene" of 5- carboxyl -5- ethyl, 5- carboxyl -6- methyl Bicyclic [2.2.1] hept-2-ene" of bicyclic [2.2.1] hept-2-ene", 5- carboxyl -6- ethyl.
In concrete example of the invention, polycyclic type unsaturated dicarboxylic compound is 5,6- dicarboxylic acids, two ring [2.2.1] hept- 2- alkene.In concrete example of the invention, polycyclic type unsaturated dicarboxylic acid anhydride compound is aforementioned polycyclic type unsaturated dicarboxylic Close the anhydride compound of object.
In preferred embodiment of the invention, unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides compound (a1) are acrylic acid, first Base acrylic acid, maleic anhydride, 2- methacryloyloxyethyl succinate and 2- methacryl base oxethyl hexahydrobenzene two Formic acid.The equal unsaturated carboxylic acids or unsaturated carboxylic acid anhydrides compound (a1) can the independent or a variety of uses of mixing.
The usage amount of polymerization compound based on alkali soluble resin (A-2) is 100 parts by weight, and of the invention contains epoxy The usage amount of the unsaturated compound (a2) of base is 10 to 50 parts by weight, preferably 12 to 45 parts by weight, more preferably 15 to 40 weights Measure part.The concrete example of the above-mentioned unsaturated compound (a2) containing epoxy group are as follows: (methyl) acrylate compounds containing epoxy group, Alpha-alkyl acrylate compounds, glycidyl ether compounds containing epoxy group.
In concrete example of the invention, (methyl) acrylate compounds containing epoxy group are (methyl) acrylic acid epoxy third Ester, (methyl) acrylic acid 2- methyl polyglycidyl, (methyl) acrylic acid 3,4- epoxy butyl ester, (methyl) acrylic acid 6,7- epoxy heptan Ester, (methyl) acrylic acid 3,4- epoxy cyclohexyl, (methyl) acrylic acid 3,4- epoxycyclohexanecarboxylate.
In concrete example of the invention, the alpha-alkyl acrylate compounds containing epoxy group are α-ethylacrylate epoxy third Ester, α-n-propyl Glycidyl Acrylate, α-n-butyl polyglycidyl, α-ethylacrylate 6,7- epoxy heptyl ester.
In concrete example of the invention, glycidyl ether compounds are o- vinyl benzene methyl glycidyl ethers (o- Vinylbenzylglycidylether), m- vinyl benzene methyl glycidyl ethers (m- Vinylbenzylglycidylether), p- vinyl benzene methyl glycidyl ethers (p- vinylbenzylglycidylether)。
Unsaturated compound (a2) preferred embodiment of the present invention containing epoxy group is glycidyl methacrylate, (methyl) Acrylic acid 3,4- epoxycyclohexanecarboxylate, methacrylic acid 6,7- epoxy heptyl ester, o- vinyl benzene methyl glycidyl ethers, m- second Alkenyl benzyl glycidyl ethers and p- vinyl benzene methyl glycidyl ethers.
The usage amount of polymerization compound based on alkali soluble resin (A-2) is 100 parts by weight, other unsaturation chemical combination The usage amount of object (a3) is 0 to 85 parts by weight, preferably 10 to 80 parts by weight, more preferably 20 to 75 parts by weight.Other unsaturations The concrete example of compound (a3) is (methyl) alkyl acrylate, (methyl) acrylic acid alicyclic ester, (methyl) acrylic acid aryl Ester, unsaturated dicarboxylic diester, (methyl) hydroxyalkyl acrylate, the polyethers of (methyl) acrylate, aromatic vinyl compound and Other unsaturated compounds.
In concrete example of the invention, (methyl) alkyl acrylate is (methyl) methyl acrylate, (methyl) acrylic acid Ethyl ester, (methyl) n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) acrylic acid are different Butyl ester, (methyl) acrylic acid second level butyl ester, (methyl) acrylic acid three-level butyl ester.
In concrete example of the invention, (methyl) acrylic acid alicyclic ester is (methyl) cyclohexyl acrylate, (methyl) third Olefin(e) acid -2- methyl cyclohexyl, tricyclic [5.2.1.02,6] decyl- 8- base (methyl) acrylate are (or double for (methyl) acrylic acid Ring pentyl ester), two cyclopentyloxy ethyl ester of (methyl) acrylic acid, (methyl) isobornyl acrylate, (methyl) acrylic acid tetrahydrofuran Ester.
In concrete example of the invention, (methyl) benzyl acrylate is (methyl) phenyl acrylate, methacrylic acid Benzene methyl.
In concrete example of the invention, unsaturated dicarboxylic diester is diethyl maleate, diethyl fumarate, itaconic acid Diethylester.
In concrete example of the invention, (methyl) hydroxyalkyl acrylate is (methyl) 2-Hydroxy ethyl acrylate, (methyl) 2-hydroxypropyl acrylate.
In concrete example of the invention, the polyethers of (methyl) acrylate is polyethyleneglycol (methyl) acrylate, gathers Propylene glycol list (methyl) acrylate.
In concrete example of the invention, aromatic vinyl compound be styrene, α-methylstyrene, m- methyl styrene, P-methylstyrene, p-methoxystyrene.
In concrete example of the invention, other unsaturated compounds are acrylonitrile, methacrylonitrile, vinyl chloride, inclined dichloro Ethylene, acrylamide, Methacrylamide, ethylene ethyl ester, 1,3- butadiene, isoprene, 2,3- dimethyl 1,3- butadiene, N- N-cyclohexylmaleimide, N-phenylmaleimide, N- Benzyl base maleimide, the Malaysia N- succimide base -3- acyl Imines benzoic ether, N- succimide base -4- malimidobutanoate, N- succimide base -6- maleimide oneself Acid esters, N- succimide base -3- maleimidopropionic acid ester, N- (9- acridinyl) maleimide.
Other unsaturated compounds (a3) preferred embodiment of the invention is (methyl) methyl acrylate, (methyl) acrylic acid Butyl ester, (methyl) acrylic acid 2- hydroxy methacrylate, (methyl) acrylic acid three-level butyl ester, (methyl) benzyl acrylate, (methyl) third The bicyclic pentyl ester of olefin(e) acid, two cyclopentyloxy ethyl ester of (methyl) acrylic acid, styrene, p-methoxystyrene.It is other according to the present invention Unsaturated compound (a3) can be used alone or in combination.
Alkali soluble resin (A-2) of the invention during fabrication used solvent concrete example be alcohol, ether, glycol ethers, second Glycol alkyl ether acetate, diethylene glycol, dipropylene glycol, propylene-glycol monoalky lether, propylene glycol alkyl ether acetate, propylene glycol alkane Base ether propionic ester, aromatic hydrocarbon, ketone, ester.
In concrete example of the invention, alcohol is methanol, ethyl alcohol, benzyl alcohol, 2 phenylethyl alcohol, 3- phenyl-1-propanol.
In concrete example of the invention, ether is tetrahydrofuran.
In concrete example of the invention, glycol ethers are ethylene glycol ether, glycol monoethyl ether, ethylene glycol monoethyl ether.
In concrete example of the invention, ethylene glycol alkyl ether acetate is 2-Butoxyethyl acetate, ethylene glycol ethyl ether vinegar Acid esters, glycol methyl ether acetate.
In concrete example of the invention, diethylene glycol is diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol list Butyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethylmethyl ether.
In concrete example of the invention, dipropylene glycol is dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol two Methyl ether, dipropylene glycol diethyl ether, dipropylene glycol ethyl methyl ether.
In concrete example of the invention, propylene-glycol monoalky lether is propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol list Propyl ether, propylene glycol monobutyl ether.
In concrete example of the invention, propylene glycol alkyl ether acetate is propylene glycol methyl ether acetate, propylene-glycol ethyl ether vinegar Acid esters, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate.
In concrete example of the invention, propylene glycol alkyl ether propionic ester is propylene glycol monomethyl ether acetate, propylene-glycol ethyl ether third Acid esters, propylene glycol propyl ether propionic ester, propandiol butyl ether propionic ester.
In concrete example of the invention, aromatic hydrocarbon is toluene, dimethylbenzene.
In concrete example of the invention, ketone is methyl ethyl ketone, cyclohexanone, diacetone alcohol.
In concrete example of the invention, ester is methyl acetate, ethyl acetate, propyl acetate, butyl acetate, 2 hydroxy propanoic acid Ethyl ester, 2- hydroxy-2-methyl methyl propionate, 2- hydroxy-2-methyl ethyl propionate, glycolic acid methyl esters, ethyl glycolate, glycolic acid Butyl ester, methyl lactate, propyl lactate, butyl lactate, 3- hydroxy methyl propionate, 3- hydroxypropionate, 3- hydracrylic acid propyl ester, 3- hydracrylic acid butyl ester, 2- hydroxy-3-methyl methyl butyrate, methoxy menthyl acetate, ethyl methoxyacetate, methoxyacetic acid Butyl ester, ethoxy acetate, ethoxy ethyl acetate, ethoxyacetic acid propyl ester, ethoxyacetic acid butyl ester, propoxyl group acetic acid first Ester, propoxyl group ethyl acetate, propoxyl group propyl acetate, propoxyl group butyl acetate, butoxy acetic acid methyl esters, butoxy acetic acid second Ester, butoxy acetic acid propyl ester, butoxy acetic acid butyl ester, 3- methoxybutyl acetic acid esters, 2- methoxy methyl propionate, 2- methoxyl group Ethyl propionate, 2- methoxy propyl propyl propionate, 2- methoxy propyl acid butyl ester, 2- ethoxypropanoate, 2- ethoxyl ethyl propionate, 2- ethoxy-c propyl propionate, 2- ethoxy-c acid butyl ester, 2- butoxy methyl propionate, 2- butoxy methyl propionate, 2- butoxy Ethyl propionate, 2- butoxy propyl propionate, 2- butoxy butyl propionate, 3- methoxy methyl propionate, 3- methoxypropionate, 3- methoxy propyl propyl propionate, 3- methoxy propyl acid butyl ester, 3- ethoxypropanoate, 3- ethoxyl ethyl propionate, 3- ethyoxyl Propyl propionate, 3- ethoxy-c acid butyl ester, 3- propoxyl group methyl propionate, 3- propoxyl group ethyl propionate, 3- propoxyl group propyl propionate, 3- propoxyl group butyl propionate, 3- butoxy methyl propionate, 3- butoxy ethyl propionate, 3- butoxy propyl propionate, 3- butoxy Butyl propionate.
Used preferred solvents are diethylene glycol dimethyl ether, the third two to alkali soluble resin (A-2) of the invention during fabrication Alcohol methyl ether acetate.According to the present invention alkali soluble resin (A-2) during fabrication can be used alone or in combination using solvent.
Used polymerization initiators, concrete example are even to alkali soluble resin (A-2) according to the present invention during fabrication Nitrogen compound or peroxide.
The concrete example of azo-compound be 2,2'- azobis isobutyronitrile, 2,2'- azo bis- (2,4- methyl pentane nitriles), 2, Double -2- the methylbutyronitriles of 2'- azo bis- (4- methoxyl group -2,4- methyl pentane nitriles), 2,2'- azo, bis- (the 4- cyano of 4,4'- azo Valeric acid), dimethyl 2,2'- azo bis- (2 Methylpropionic acid esters), 2,2'- azo it is bis- (4- methoxyl group -2,4- methyl pentane nitrile).
The concrete example of peroxide be dibenzoyl peroxide, dilauroyl peroxide, tert-butyl hydroperoxide trimethylacetic acid ester, 1, Bis- (tert-butyl hydroperoxide) hexamethylenes of 1-, hydrogen peroxide.
Used polymerization initiators can make alkali soluble resin (A-2) alone or in combination during fabrication according to the present invention With.
The weight average molecular weight of alkali soluble resin (A-2) of the invention is generally 3,000 to 100,000, preferably 4,000 to 80,000, more preferably 5,000 to 60,000.The molecular weight of alkali soluble resin (A-2) adjusts, and single tree can be used Rouge also can be used the resin of two or more different molecular weight and be used to reach.
In a specific example of the present invention, the usage amount based on the alkali soluble resin (A) is 100 parts by weight, which can The usage amount of soluble resin (A-2) is 0 to 70 parts by weight；Preferably 0 to 50 parts by weight；It is more preferably 0 to 30 parts by weight.
Compound (B) with ethylene unsaturated group
It includes following formula (b-I) and/or formula (b-II) that according to the present invention this, which has the compound (B) of ethylene unsaturated group, The compound (B-2) of compound represented (B-1) and other unsaturated groups containing ethylene.
Compound (B-1)
According to the present invention should include shown in the structure such as following formula (b-I) of compound (B-1) and formula (b-II):
Figure BDA0001070387350000151
In formula (b-I), R21And R22Hydrogen atom or methyl are respectively independently represented, p indicates 0 to 4 number；
Figure BDA0001070387350000161
In formula (b-II), R23And R24Hydrogen atom or methyl are respectively independently represented, m indicates 0 to 4 number.
P and m indicates that alkylene oxide group per molecule is averaged adduct number in formula (b-I) and formula (b-II).
The concrete example of above-mentioned formula (b-I) can be p- cumylphenyl (methyl) acrylate and p- cumenyl phenoxy group Ethyl (methyl) acrylate etc., wherein with p- cumylphenyl (methyl) acrylate and p- cumenyl Phenoxyethyl (methyl) acrylate is preferred.
The concrete example of above-mentioned formula (b-II) can be o- phenyl (methyl) acrylate, m- phenyl (methyl) propylene Acid esters, p- phenyl (methyl) acrylate, o- phenyl benzene oxygen ethyl (methyl) acrylate, m- phenyl benzene oxygen ethyl (first Base) acrylate and p- phenyl benzene oxygen ethyl (methyl) acrylate etc., wherein with o- phenyl (methyl) acrylate and O- phenyl benzene oxygen ethyl (methyl) acrylate is preferred.
Based on 100 parts by weight of alkali soluble resin (A), the usage amount of compound (B-1) is 15 parts by weight to 100 weight Part, preferably 20 parts by weight to 90 parts by weight, more preferably 25 parts by weight to 80 parts by weight.If, can be into when using compound (B-1) One step improve photosensitive polymer combination be formed by film refractive index and with molybdenum adherence.
Though it is reluctant to be limited by theory, it is believed that because compound (B-1) has aromatic ring structure, therefore refractive index is higher.In addition, Because compound (B-1) has steric hindrance structure, shrinking percentage can be reduced and mitigate film internal stress, therefore have preferable molybdenum close Property.
Other compounds (B-2) with ethylene unsaturated group
The compound (B) of the unsaturated group containing ethylene additionally comprises the compound (B-2) of other unsaturated groups containing ethylene, It is selected from the compound with 1 ethylene unsaturated group or the change with 2 or more (containing 2) ethylene unsaturated groups Close object.
The compound with 1 ethylene unsaturated group above-mentioned be may include, but are not limited to (methyl) acryloyl morpholine, (methyl) acrylic acid -7- amino -3,7- dimethyl monooctyl ester, isobutoxymethyl (methyl) acrylamide, (methyl) acrylic acid are different Bornyl 2-ethoxyethyl acetate, (methyl) isobornyl acrylate, (methyl) acrylic acid-2-ethyl caproite, ethyl diethylene glycol (methyl) Acrylate, t-octyl (methyl) acrylamide, diacetone (methyl) acrylamide, (methyl) dimethyl aminoethyl Ester, (methyl) dodecylacrylate, (methyl) acrylic acid dicyclopentenyl oxygroup ethyl ester, (methyl) acrylic acid dicyclopentenyl Ester, nitrogen, nitrogen-dimethyl (methyl) acrylamide, (methyl) acrylic acid tetrachloro phenyl ester, (methyl) acrylic acid -2- tetrachloro phenoxy group Ethyl ester, (methyl) tetrahydrofurfuryl acrylate [tetrahydrofurfuryl (meth) acrylate], (methyl) acrylic acid tetrabromo Phenyl ester, (methyl) acrylic acid -2- tetrabromo phenoxy ethyl, (methyl) acrylic acid -2- Trichlorophenoxy ethyl ester, (methyl) acrylic acid Tribromophenyl, (methyl) acrylic acid -2- tribromophenoxy ethyl ester, 2- hydroxyl-(methyl) ethyl acrylate, 2- hydroxyl-(methyl) Propyl acrylate, caprolactam, nitrogen-vinyl pyrrolidone, (methyl) phenoxyethyl acrylate, (methyl) propylene Sour pentachlorophenyl ester, (methyl) acrylic acid pentabromo- phenyl ester, poly- single (methyl) acrylic acid second diester, poly- single (methyl) acrylic acid the third two Ester, (methyl) acrylic acid norbornene ester etc..The compound with 1 ethylene unsaturated group above-mentioned generally can be individually a kind of or mixed Close a variety of uses.
The compound with 2 or more (containing 2) ethylene unsaturated groups above-mentioned is including but not limited to ethylene glycol two (methyl) acrylate, two (methyl) acrylic acid dicyclopentenyl esters, triethylene glycol two (methyl) acrylate, tetraethylene glycol two (methyl) acrylate, three (2- hydroxyethyl) isocyanic acid two (methyl) acrylate, three (2- hydroxyethyl) isocyanic acids, three (first Base) acrylate, caprolactone modification three (2- hydroxyethyl) isocyanic acid three (methyl) acrylate, three (methyl) acrylic acid three Methylol propyl ester, three (methyl) acrylic acid trihydroxy methyl propyl ester of ethylene oxide (abbreviation EO) modification, propylene oxide modification are (referred to as PO three (methyl) acrylic acid trihydroxy methyl propyl ester, tripropylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) propylene) Acid esters, 1,4- butanediol two (methyl) acrylate, 1,6-hexylene glycols two (methyl) acrylate, pentaerythrite three (methyl) third Olefin(e) acid ester, pentaerythrite four (methyl) acrylate, polyester two (methyl) acrylate, polyethylene glycol two (methyl) acrylic acid Ester, dipentaerythritol six (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol four (methyl) third The dipentaerythritol five (methyl) that olefin(e) acid ester, the dipentaerythritol six (methyl) acrylate of caprolactone modification, caprolactone modify Acrylate, four (methyl) acrylic acid, two trihydroxy methyl propyl ester [di (trimethylolpropane) tetra (meth) Acrylate], ethane via epoxyethane modification bisphenol-A two (methyl) acrylate, through propylene oxide modify bisphenol-A two (methyl) Acrylate, hydrogenated bisphenol A two (methyl) acrylate of ethane via epoxyethane modification, the hydrogenated bisphenol A through propylene oxide modification The Bisphenol F two that two (methyl) acrylate, glycerol three (methyl) acrylate through propylene oxide modification, ethane via epoxyethane modify (methyl) acrylate, novolaks polyglycidyl ether (methyl) acrylate etc..It is above-mentioned that there are 2 or more (containing 2) The compound of ethylene unsaturated group generally can the individually a kind of or a variety of uses of mixing.
In a specific example of the present invention, the usage amount based on the alkali soluble resin (A) is 100 parts by weight, this contains second The usage amount of the compound (B) of alkene unsaturated group is 15 parts by weight to 300 parts by weight, preferably 25 parts by weight to 280 weight Part, more preferably 40 parts by weight to 250 parts by weight.
Light initiator (C)
There is no particular restriction for smooth initiator (C) according to the present invention, in one embodiment of this invention, may include but not It is limited to O- acyl group oxime compound, triazine based compound, vinylbenzene ketone compounds, diimidazole class compound, hexichol first Ketone compounds, α-cyclohexadione compounds, ketols compound, keto-alcohol ether compound, acyl phosphine oxide class compound, quinones Compound, containing halogen-based compounds, peroxide etc., following division it.
The concrete example of above-mentioned O- acyl group oxime compound are as follows: 1- [4- (phenyl) phenyl]-heptane -1,2- diketone 2- (O- benzoyl group oxime), 1- [4- (phenyl) phenyl]-octane -1,2- diketone 2- (O- benzoyl group oxime), 1- [4- (benzoyl group) benzene Base]-heptane -1,2- diketone 2- (O- benzoyl group oxime), 1- [9- ethyl -6- (2- methyl benzoyl group) -9H- carbazole -3- substituent group] - Ethane ketone 1- (O- acetyl group oxime), 1- [9- ethyl -6- (3- methyl benzoyl group) -9H- carbazole -3- substituent group]-ethane ketone 1- (O- Acetyl group oxime), 1- [9- ethyl -6- benzoyl group -9H- carbazole -3- substituent group]-ethane ketone 1- (O- acetyl group oxime), ethane ketone -1- [9- ethyl -6- (2- methyl -4- tetrahydrofuran base benzoyl group) -9H- carbazole -3- substituent group] -1- (O- acetyl group oxime), ethane Ketone -1- [9- ethyl -6- (2- methyl -4- THP trtrahydropyranyl benzoyl group) -9H- carbazole -3- substituent group] -1- (O- acetyl group oxime), Ethane ketone -1- [9- ethyl -6- (2- methyl -5- tetrahydrofuran base benzoyl group) -9H- carbazole -3- substituent group] -1- (O- acetyl group Oxime), ethane ketone -1- [9- ethyl -6- (2- methyl -5- THP trtrahydropyranyl benzoyl group) -9H- carbazole -3- substituent group] -1- (O- second Acyl group oxime), ethane ketone -1- [9- ethyl -6- (2- methyl -4- tetrahydrofuran base methoxybenzene acyl group) -9H- carbazole -3- replace Base] -1- (O- acetyl group oxime), ethane ketone -1- [9- ethyl -6- (2- methyl -4- THP trtrahydropyranyl methoxybenzene acyl group) -9H- click Azoles -3- substituent group] -1- (O- acetyl group oxime), ethane ketone -1- [9- ethyl -6- (2- methyl -5- tetrahydrofuran base methoxyl group benzoyl Base) -9H- carbazole -3- substituent group] -1- (O- acetyl group oxime), ethane ketone -1- [9- ethyl -6- (2- methyl -5- THP trtrahydropyranyl Methoxybenzene acyl group) -9H- carbazole -3- substituent group] -1- (O- acetyl group oxime), ethane ketone -1- [9- ethyl -6- { 2- methyl -4- (2,2- dimethyl -1,3- dioxolane base) benzoyl group } -9H- carbazole -3- substituent group] -1- (O- acetyl group oxime), ethane ketone - [9- ethyl -6- { 2- methyl -4- (2,2- dimethyl -1,3- dioxolane base) methoxybenzene acyl group } -9H- carbazole -3- takes 1- Dai Ji] -1- (O- acetyl group oxime) etc..
O- acyl group oxime compound above-mentioned is with 1- [4- (phenyl) phenyl]-octane -1,2- diketone 2- (O- benzoyl group Oxime) (such as OXE 01 of Ciba Specialty Chemicals), 1- [9- ethyl -6- (2- methyl benzoyl group) -9H- click Azoles -3- substituent group]-ethane ketone 1- (O- acetyl group oxime) (such as OXE 02 of Ciba Specialty Chemicals), second Alkanone -1- [9- ethyl -6- (2- methyl -4- tetrahydrofuran methoxybenzene acyl group) -9H- carbazole -3- substituent group] -1- (O- acetyl Base oxime), ethane ketone -1- [9- ethyl -6- { 2- methyl -4- (2,2- dimethyl -1,3- dioxolane base) methoxyl group benzoyl Base } -9H- carbazole -3- substituent group] -1- (O- acetyl group oxime) etc. is preferable.Above-mentioned O- acyl group oxime compound can be individually a kind of Or a variety of uses of mixing, end is depending on actual needs.
Above-mentioned triazine based compound may include but be not limited to vinyl-halogenated methyl-s- triazine compound, 2- (naphtho- -1- substituent group) -4,6- pairs-halogenated methyl-s- triazine compound and 4- (p- aminophenyl) two-halogen of -2,6- For methyl-s- triazine compound etc..
Vinyl above-mentioned-halogenated methyl-s- triazine compound concrete example are as follows: bis- (the trichloromethyl) -6- of 2,4- P-methoxystyrene base-s- triazine, 2,4- bis- (trichloromethyl) -3- (p- dimethylaminophenyl -1,3- fourth two of 1- Alkenyl)-s- triazine, 2- trichloromethyl -3- amino -6- p-methoxystyrene base-s- triazine etc..
The concrete example of 2- (naphtho- -1- substituent group) -4,6- above-mentioned pairs-halogenated methyl-s- triazine compound are as follows: 2- (naphtho- -1- substituent group) -4,6- is double-and trichloromethyl-s- triazine, 2- (4- methoxyl group-naphtho- -1- substituent group) -4,6- be double - Trichloromethyl-s- triazine, 2- (4- ethyoxyl-naphtho- -1- substituent group) -4,6- pairs-trichloromethyl-s- triazine, 2- (4- butoxy-naphtho- -1- substituent group) -4,6- pairs-trichloromethyl-s- triazine, 2- [4- (2- methoxy ethyl)-naphtho- - 1- substituent group] -4,6- pairs-trichloromethyl-s- triazine, 2- [4- (2- ethoxyethyl group)-naphtho- -1- substituent group] -4,6- Double-trichloromethyl-s- triazine, 2- [4- (2- butoxyethyl group)-naphtho- -1- substituent group] -4,6- pairs-trichloromethyl-s- Triazine, 2- (2- methoxyl group-naphtho- -1- substituent group) -4,6- pairs-trichloromethyl-s- triazine, 2- (6- methoxyl group -5- Methyl-naphtho- -2- substituent group) -4,6- pairs-trichloromethyl-s- triazine, 2- (6- methoxyl group-naphtho- -2- substituent group) -4, 6- is bis--and trichloromethyl-s- triazine, 2- (5- methoxyl group-naphtho- -1- substituent group) -4,6- be double-three azepine of trichloromethyl-s- Benzene, 2- (4,7- dimethoxy-naphtho- -1- substituent group) -4,6- pairs-trichloromethyl-s- triazine, 2- (6- ethyoxyl-naphthalene And -2- substituent group) -4,6- pairs-trichloromethyl-s- triazine, 2- (4,5- dimethoxy-naphtho- -1- substituent group) -4,6- Double-trichloromethyl-s- triazine etc..
The concrete example of 4- (p- aminophenyl) -2,6- two-halogenated methyl-s- triazine compound above-mentioned are as follows: 4- [p- N, N- bis- (ethoxy carbonyl methyl) aminophenyl] (the trichloromethyl)-s- of -2,6- two triazine, 4- [ortho-methyl - P- N, N- bis- (ethoxy carbonyl methyl) aminophenyl] (the trichloromethyl)-s- of -2,6- two triazine, 4- [p- N, N- bis- (chloroethyl) aminophenyl] (the trichloromethyl)-s- of -2,6- two triazine, 4- [ortho-methyl-p- N, N- bis- (chloroethyl) ammonia Base phenyl] (the trichloromethyl)-s- of -2,6- two triazine, 4- (p- N- chloroethyl amino phenyl) -2,6- two (trichloromethyl) - S- triazine, 4- (p- N- ethoxycarbonylmethylamino phenyl) (the trichloromethyl)-s- of -2,6- two triazine, 4- are [p- N, N- bis- (phenyl) aminophenyl] (the trichloromethyl)-s- of -2,6- two triazine, 4- (p- N- chloroethyl amino carbonyl phenyl Base) (the trichloromethyl)-s- of -2,6- two triazine, 4- [p- N- (p- methoxyphenyl) carbonylamino phenyl] -2,6- two (trichloromethyl)-s- triazine, 4- [m- N, N- bis- (ethoxy carbonyl methyl) aminophenyl] -2,6- two (trichloromethyl) - S- triazine, 4- [m- bromo- p- N, N- bis- (ethoxy carbonyl methyl) aminophenyl] -2,6- two (trichloromethyl)-s- three Pyridine, three azepine of 4- [m- chloro- p- N, N- bis- (ethoxy carbonyl methyl) aminophenyl] -2,6- two (trichloromethyl)-s- Benzene, 4- [m- fluoro- p- N, N- bis- (ethoxy carbonyl methyl) aminophenyl] (the trichloromethyl)-s- of -2,6- two triazine, 4- [o- bromo- p- N, N- bis- (ethoxy carbonyl methyl) aminophenyl] (the trichloromethyl)-s- of -2,6- two triazine, 4- are [o- Two (trichloromethyl)-s- triazine of chloro- p- N, N- bis- (ethoxy carbonyl methyl) aminophenyl -2,6-, 4- are [o- fluoro- p- N, N- bis- (ethoxy carbonyl methyl) aminophenyl] (the trichloromethyl)-s- of -2,6- two triazine, 4- [o- bromo- p- N, N- Two (chloroethyl) aminophenyls] (the trichloromethyl)-s- of -2,6- two triazine, 4- [o- chloro- p- N, N- bis- (chloroethyl) ammonia Base phenyl] (the trichloromethyl)-s- of -2,6- two triazine, 4- [o- fluoro- p- N, N- bis- (chloroethyl) aminophenyl] -2,6- Two (trichloromethyl)-s- triazines, 4- [m- bromo- p- N, N- bis- (chloroethyl) aminophenyl] -2,6- two (trichloromethyl) - S- triazine, 4- [m- chloro- p- N, N- bis- (chloroethyl) aminophenyl] (the trichloromethyl)-s- of -2,6- two triazine, 4- [m- fluoro- p- N, N- bis- (chloroethyl) aminophenyl] (the trichloromethyl)-s- of -2,6- two triazine, 4- (m- bromo- p- N- Ethoxycarbonylmethylamino phenyl) (the trichloromethyl)-s- of -2,6- two triazine, 4- (m- chloro- p- N- ethoxy carbonyl Methylamino phenyl) (the trichloromethyl)-s- of -2,6- two triazine, 4- (m- fluoro- p- N- ethoxycarbonylmethylamino benzene Base) (the trichloromethyl)-s- of -2,6- two triazine, 4- (o- bromo- p- N- ethoxycarbonylmethylamino phenyl) -2,6- two (trichloromethyl)-s- triazine, 4- (o- chloro- p- N- ethoxycarbonylmethylamino phenyl) -2,6- two (trichloromethyl) - S- triazine, 4- (o- fluoro- p- N- ethoxycarbonylmethylamino phenyl) (the trichloromethyl)-s- of -2,6- two triazine, 4- (m- bromo- p- N- chloroethyl amino phenyl) (the trichloromethyl)-s- of -2,6- two triazine, 4- (m- chloro- p- N- chloroethene Base aminophenyl) (the trichloromethyl)-s- of -2,6- two triazine, 4- (m- fluoro- p- N- chloroethyl amino phenyl) -2,6- two (trichloromethyl)-s- triazine, three azepine of 4- (o- bromo- p- N- chloroethyl amino phenyl) -2,6- two (trichloromethyl)-s- Benzene, 4- (o- chloro- p- N- chloroethyl amino phenyl) (the trichloromethyl)-s- of -2,6- two triazine, 4- (o- fluoro- p- N- chlorine Ethylamino phenyl) (the trichloromethyl)-s- of -2,6- two triazine, [[N, N- are bis- by the bromo- 4- of 3- by bis- (the trichloromethyl) -6- of 2,4- (ethoxy carbonyl methyl) amino] phenyl] -1,3,5- triazine etc..
Aforementioned triazine based compound with 4- [m- bromo- p- N, N- bis- (ethoxy carbonyl methyl) aminophenyl] -2, Bis- (trichloromethyl) -6- p-methoxystyrene base-s- triazines of (the trichloromethyl)-s- of 6- bis- triazine, 2,4- etc. are Preferably.Above-mentioned triazine based compound can be individually a kind of or mixes a variety of uses, and end is depending on actual needs.
The concrete example of above-mentioned vinylbenzene ketone compounds are as follows: to dimethylamino vinylbenzene ketone, α, the oxidation of α '-dimethoxy Azo vinylbenzene ketone, 2,2'- dimethyl-2- phenyl vinylbenzene ketone, p- methoxybenzene ethane ketone, 2- methyl-1-[4- (first sulphur Base) phenyl] -2- good fortune quinoline generation -1- acetone, 2- benzyl -2-N, N- dimethylamino -1- (4- morphlinophenyl) -1- butanone etc..Before The vinylbenzene ketone compounds stated with 2- methyl-1-[4- (methyl mercapto) phenyl]-2- good fortune quinoline generation-1- acetone, 2- benzyl-2-N, N- dimethylamino -1- (4- morphlinophenyl) -1- butanone etc. is preferable.Above-mentioned vinylbenzene ketone compounds can it is individually a kind of or A variety of uses are mixed, end is depending on actual needs.
The concrete example of above-mentioned diimidazole class compound are as follows: bis- (o- the chlorphenyl) -4,4' of 2,2'-, 5,5'- tetraphenyl two Imidazoles, 2,2'- bis- (ortho-fluorophenyl base) -4,4', 5,5'- tetraphenyl diimidazole, 2,2'- bis- (ortho-methyl phenyl) -4,4', 5, Bis- (o- the methoxyphenyl) -4,4' of 5'- tetraphenyl diimidazole, 2,2'-, bis- (the o- ethyls of 5,5'- tetraphenyl diimidazole, 2,2'- Phenyl) -4,4', bis- (p- the methoxyphenyl) -4,4' of 5,5'- tetraphenyl diimidazole, 2,2'-, 5,5'- tetraphenyl diimidazole, 2, Bis- bis- (2- the chlorphenyl) -4,4' of (2,2', 4,4'- tetramethoxy phenyl) -4,4', 5,5'- tetraphenyl diimidazole, 2,2'- of 2'-, Bis- (2,4 dichloro benzene base) -4,4', 5,5'- tetraphenyl diimidazoles of 5,5'- tetraphenyl diimidazole, 2,2'- etc..Diimidazole above-mentioned Class compound is preferable with bis- (2,4 dichloro benzene base) -4,4', 5,5'- the tetraphenyl diimidazoles of 2,2'-.Above-mentioned diimidazole class Conjunction object can be individually a kind of or mixes a variety of uses, and end is depending on being actually needed.
The concrete example of above-mentioned benzophenone compound are as follows: thioxanthones, 2,4- diethyl thioxanthone, thioxanthones -4- sulfone, Bis- (dimethylamino) benzophenone of benzophenone, 4,4'-, bis- (lignocaine) benzophenone of 4,4'- etc..Benzophenone above-mentioned Class compound is preferable with bis- (lignocaine) benzophenone of 4,4'-.Above-mentioned benzophenone compound can it is individually a kind of or A variety of uses are mixed, end is depending on actual needs.
Above-mentioned α-cyclohexadione compounds concrete example are as follows: benzil, biacetyl etc..The tool of above-mentioned ketols compound Body example are as follows: diphenylhydroxyethanone.The concrete example of above-mentioned keto-alcohol ether compound are as follows: diphenylhydroxyethanone methyl ether, diphenylhydroxyethanone second Ether, diphenylhydroxyethanone isopropyl ether etc..The concrete example of above-mentioned acyl phosphine oxide class compound are as follows: 2,4,6- trimethyl benzoyl hexichol Base phosphine oxide, double-(2,6- dimethoxy benzoyl) -2,4,4- trimethylpentyl phosphine oxide etc..Above-mentioned quinones Concrete example are as follows: anthraquinone, 1,4- naphthoquinones etc..The above-mentioned concrete example containing halogen-based compounds are as follows: chloroacetophenone, trisbromomethyl Benzene sulfone, three (trichloromethyl)-s- triazines etc..The concrete example of above-mentioned peroxide are as follows: di-t-butyl peroxide etc.. Above-mentioned α-cyclohexadione compounds, ketols compound, keto-alcohol ether compound, acyl phosphine oxide class compound, quinones chemical combination Object, containing halogen-based compounds, peroxide etc. can the individually a kind of or a variety of uses of mixing, depending on end view is actually needed.
The usage amount of light initiator (C) of the invention can deploy according to need, in a specific example of the present invention, be based on the alkali The usage amount of soluble resin (A) is 100 parts by weight, and the usage amount of the light initiator (C) is 10 to 100 parts by weight, preferably 12 to 90 parts by weight, more preferably 15 to 80 parts by weight.
Solvent (D)
Solvent (D) according to the present invention is that can be completely dissolved with other organic principles and its volatility must be high to normal Pressure only needs a little heat it can be made to evaporate from dispersion liquid.Therefore solvent of its boiling point lower than 150 DEG C most often makes under normal pressure With these solvents include aromatic system, such as benzene, toluene and dimethylbenzene；Alcohol system, such as methanol and ethyl alcohol；Ethers system, such as ethylene glycol Single propyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, glycol monoethyl ether, ethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethyl two Alcohol ether, butyl；Esters system, such as glycol methyl ether acetate, ethylene glycol ether acetate, propylene glycol monomethyl ether acetic acid Ester, propylene-glycol ethyl ether acetate, propylene glycol propyl ether acetate, 3- ethoxyl ethyl propionate；Ketone system, such as methyl ethyl ketone and acetone. Wherein with diethylene glycol dimethyl ether, propylene glycol methyl ether acetate and 3- ethoxyl ethyl propionate individually or both and with preferable, It is best to the stability in storage of photosensitive polymer combination.
The usage amount of solvent (D) of the invention can deploy according to need, solvable based on the alkali in a specific example of the present invention Property resin (A) usage amount be 100 parts by weight, the usage amount of solvent (D) is 500 parts by weight to 3000 parts by weight, preferably 600 Parts by weight are to 2800 parts by weight, more preferably 700 parts by weight to 2500 parts by weight.
Silane compound (E)
Photosensitive polymer combination of the invention includes silane compound (E).Silane compound (E) has such as formula (I) institute The silane compound (E-1) for the structure shown:
Figure BDA0001070387350000221
In formula (I), A respectively stands alone as singly-bound, alkylidene (alkylene) or secondary aryl (arylene), and B is respectively independent To have organic group, hydrogen atom, alkyl, aryl or the-OR of diphenylphosphino, wherein R is the alkyl or phenyl that carbon number is 1 to 6,
Wherein, at least one B is the organic group for having diphenylphosphino, at least one B is-OR, and when B is-OR, with The A of B connection is singly-bound.
The concrete example of silane compound (E-1) may include [4- [dimethyl-(1- methyl ethoxy) silicon substrate] phenyl] hexichol Base phosphine ([4-dimethyl (1-methylethoxy) sily] phenyl) diphenyl phosphine), [2- [dimethyl- (1- methyl ethoxy) silicon substrate] phenyl] diphenylphosphine ([2- [dimethyl (1-methylethoxy) silyl] phenyl] Diphenylphosphine), [2- (methoxyl group diphenyl silicon substrate) phenyl] diphenylphosphine ([2- (methoxydiphenylsilyl) phenyl] diphenyl phosphine), [(ethyoxyl time silicon substrate) three (methylene)] three [diphenylphosphine] ([(ethoxysilylidyne) tris (methylene)] tris [diphenyl phosphine]), [(second Oxygroup dimethyl silicon substrate) methylene] bis- [diphenylphosphines] ([(ethoxydimethylsilyl) methylene] bis [diphenyl phosphine]), [2- (ethyoxyl dimethyl silicon substrate) ethyl] diphenylphosphine ([2- (ethoxydimethylsilyl) ethyl] diphenylphosphine), [3- (dimethyl phenoxy silicon substrate) propyl] hexichol Base phosphine ([3- (dimethylphenoxysilyl) propyl] diphenyl phosphine), [(dimethyl phenoxy silicon substrate) Methyl] diphenylphosphine ([(dimethylphenoxysilyl) methyl] diphenylphosphine), [4- (ethyoxyl diformazan Base silicon substrate) phenyl] diphenylphosphine ([4- (ethoxydimethylsilyl) phenyl] diphenylphosphine), [2- (two Methylphenoxy silicon substrate) ethyl] diphenylphosphine ([2- (dimethylphenoxy silyl) ethyl] Diphenylphosphine), [3- (ethyoxyl dimethyl silicon substrate) propyl] diphenylphosphine ([3- (ethoxydimethylsilyl) propyl] diphenylphosphine), [(ethyoxyl dimethyl silicon substrate) methyl] diphenyl Phosphine ([(ethoxydimethylsilyl) methyl] diphenylphosphine), [(diethoxy silylene) bis- (methylenes Base)] bis- [diphenylphosphines] ([(diethoxysilylene) bis (methylene)] bis [diphenyl phosphine]), [(diethoxy silylene) -2,1- diethyl subunit] bis- [diphenylphosphines] ([(diethoxysilylene) di-2,1- Ethanediyl] bis [diphenyl phosphine]), [4- (diethoxymethyl silicon substrate) phenyl] diphenylphosphine ([4- (diethoxymethylsilyl) phenyl] diphenylphosphine), [(diethoxy silylene) -3,1- dipropyl is sub- Base] bis- [diphenylphosphines] ([(diethoxysilylene) di-3,1-propane diyl] bis [diphenyl Phosphine]), [3- (diethoxymethyl silicon substrate) propyl] diphenylphosphine ([3- (diethoxymethylsilyl) Propyl] diphenylphosphine), [(diethoxymethyl silicon substrate) methyl] diphenylphosphine ([(diethoxymethylsilyl) methyl] diphenylphosphine), [2- (diethoxymethyl silicon substrate) ethyl] two Phenylphosphine ([2- (diethoxymethylsilyl) ethyl] diphenylphosphine), bis- (2- diphenylphosphinoethyls)- Methylsilyl ethyl triethoxysilane (Bis (2-diphenylphosphinoethyl)-methyl Silyethyltriethoxysilane), [2- (trimethoxy silicon substrate) ethyl] diphenylphosphine ([2- (trimethoxy Silyl) ethyl] diphenylphosphine), [2- [6- (trimethoxy silicon substrate) hexyl] the third subunit of -1,3-] bis- [diphenyl Phosphine] ([2- [6- (trimethoxysilyl) hexyl] -1,3-propanediyl] bis [diphenylphosphine]), [6- (trimethoxy silicon substrate) hexyl] diphenylphosphine ([6- (trimethoxysilyl) hexyl] diphenyl phosphine), [2- [(triethoxy silicon substrate) methyl] third subunit of -1,3-] bis- [diphenylphosphines] ([2- [(triethoxysilyl) methyl] -1,3- Propanediyl] bis [diphenylphosphine]), [1- [2- (triethoxy silicon substrate) ethyl] -1,2- second subunit] it is double [diphenylphosphine] ([1- [2- (triethoxysilyl) ethyl] -1,2-ethanediyl] bis [diphenylphosphine]), [2- (trimethoxy silicon substrate) ethyl] diphenylphosphine ([2- (trimethoxysilyl) Ethyl] diphenylphosphine), [6- (triethoxy silicon substrate) hexyl] diphenylphosphine ([6- (triethoxysilyl) Hexyl] diphenylphosphine), [4- (triethoxy silicon substrate) butyl] diphenylphosphine ([4- (triethoxysilyl) Butyl] diphenylphosphine), [(triethoxy silicon substrate) methyl] diphenylphosphine ([(triethoxysilyl) Methyl] diphenylphosphine), [1- (triethoxy silicon substrate) methyl] butyl] diphenylphosphine ([1- [(triethoxysilyl) methyl] butyl] diphenyl phosphine), [1- (triethoxy silicon substrate) methyl] propyl] Diphenylphosphine ([1- [(triethoxysilyl) methyl] propyl] diphenyl phosphine), [1- methyl -2- (three Ethyl-silicone) ethyl] diphenylphosphine ([1-methyl-2- (triethoxysilyl) ethyl] diphenyl Phosphine), [7- (triethoxy silicon substrate) heptyl] diphenylphosphine ([7- (triethoxysilyl) heptyl] Diphenylphosphine), 1,1 '-[(triethoxy silicon substrate) methylene] bis- [1,1- diphenylphosphine] (1,1'- [(triethoxysilyl) methylene] bis [1,1-diphenyl phosphine], [2- (triethoxy silicon substrate) ethyl] Diphenylphosphine ([2- (triethoxysilyl) ethyl] diphenyl phosphine), [4- (triethoxy silicon substrate) phenyl] Diphenylphosphine ([4- (triethoxysilyl) phenyl] diphenylphosphine), [2- (triethoxy silicon substrate) propyl] Diphenylphosphine ([2- (triethoxysilyl) propyl] diphenylphosphine), [2- (triethoxy silicon substrate) ethyl] Diphenylphosphine ([2- (triethoxysilyl) ethyl] diphenylphosphine) or combinations of the above.
Usage amount based on alkali soluble resin (A) is 100 parts by weight, and the usage amount of silane compound (E-1) is 1 weight Part to 10 parts by weight, preferably 1.2 parts by weight to 9 parts by weight are so more preferably with 1.5 parts by weight to 8 parts by weight.If silicon is not used Hydride compounds (E-1), then photosensitive polymer combination is formed by film and molybdenum adherence and refractive index are bad.
Other silane compounds (E-2)
The silane compound (E) of photosensitive polymer combination of the invention can further include other silane compounds (E-2), and Other silane compounds (E-2) can be adherence promotor.
The adherence promotor can be used to be promoted the adhesion strength of substrate, be preferably functional silanes crosslinking agent.Preferably, should Silane crosslinker includes carboxyl, alkenyl, isocyanate group, epoxy group, amino, sulfydryl or halogen.It is in concrete example of the invention P- hydroxy phenyl trimethoxy silane, 3- methacryloxypropyl trimethoxy silane, ethylene triacetoxysilane, Ethylene trimethoxy silane, vinyltriethoxysilane, vinyl three (2- methoxyethoxy) silane, γ-isocyanates third Ethyl triethoxy silicane alkane, 3- glycidoxypropyltrime,hoxysilane, 2- (3,4- 7-oxa-bicyclo[4.1.0 base) ethyl trimethoxy Silane, 3- glycidoxypropyl group dimethyl methoxy silane, 3- TSL 8330, N- (2- amino-ethyl)- 3- TSL 8330, N- (2- amino-ethyl) -3- aminopropylmethyldimethoxysilane, 3- mercapto propyl front three Oxysilane, 3- r-chloropropyl trimethoxyl silane, 3- chloropropylmethyldimethoxysilane.On the other hand, including but not limited to Trade name SZ 6030 (Dow Corning Toray Silicone system) and trade name KBE-903, KBE-603, KBE-403 With the then auxiliary agent such as KBM-403 (SHIN-ETSU HANTOTAI's chemistry system).Then auxiliary agent can be used alone or as a mixture for this.
Usage amount based on alkali soluble resin (A) is 100 parts by weight, and the usage amount of other silane compounds (E-2) is 0 Parts by weight are to 11 parts by weight.Usage amount based on alkali soluble resin (A) is 100 parts by weight, the usage amount of silane compound (E) It can be 1 parts by weight to 12 parts by weight, preferably 1.2 parts by weight to 11 parts by weight are so more with 1.5 parts by weight to 10 parts by weight It is good.
Inorganic particulate (F)
Photosensitive polymer combination of the invention includes inorganic particulate (F).Inorganic particulate (F) according to the present invention is with The oxide of column IV element is principal component, by the inorganic particulate (F) with a high refractive index is added, be can be further improved thin The refractive index of film.
In a specific example of the present invention, wherein the particle size of the inorganic particulate (F) is 1nm to 100nm.The partial size Measurement method can be known measurement method, such as be measured by dynamic light scattering particle, and partial size is preferably 1nm extremely 50nm；More preferably 5nm to 15nm.When partial size is less than 1nm, obtained film is easy to happen secondary agglutination, and there may be Albefaction；When partial size is greater than 100nm, then the uniformity of formed film surface may be influenced.
In concrete example of the invention, the oxide particle that can be provided as inorganic particulate (F) is preferably titanium oxide, oxidation The compound particle of zirconium, hafnium oxide and these metal oxides and silica and tin oxide.It is wherein more preferably titanium oxide or oxygen Change zirconium, that is, tetrels is titanium in the inorganic particulate (F) or zirconium object is preferred.
On the other hand, the crystal form of titanium oxide exists simultaneously Detitanium-ore-type (Anatase) and rutile-type (Rutile), Preferably rutile-type, with high refractive index and excellent light resistance.
Furthermore it since titanium oxide has photocatalytic activity, therefore is difficult to as optical application, therefore is preferably covered with silica Particle surface.
Inorganic particulate (F) according to the present invention can be powder type or disperse oxide particle in decentralized medium Dispersion sol form.The decentralized medium such as methanol, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), cyclohexanone, N- methyl -2- pyrroles Alkanone, propylene glycol monomethyl ether, ethoxy ethanol.
In a specific example of the present invention, commercially available Titanium particles are Japan's C.I.Kasei system, NanoTek TiO2(point Powder is methyl iso-butyl ketone (MIBK), Detitanium-ore-type)；South Korea's NanoCMS system, (dispersing agent is ethyoxyl second to Lot No.:S111109 Alcohol, rutile-type)；Wave catalyst chemical conversion system, Red Lake series Japanese day (dispersing agent is methanol, Detitanium-ore-type)；Tayca Manufacture, TS series (dispersing agent is methyl ethyl ketone, rutile-type).Commercially available Zirconia particles are Japan Osaka Cement Co. it manufactures, HXU-120JC (dispersing agent is methyl ethyl ketone) or Mikuni Color Ltd. system, average grain diameter 13.00nm.
In concrete example of the invention, the usage amount based on the alkali soluble resin (A) is 100 parts by weight, the inorganic grain The usage amount of sub (F) is 50 parts by weight to 250 parts by weight.Preferably, the usage amount of the inorganic particulate (F) be 60 parts by weight extremely 230 parts by weight.More preferably, the usage amount of the inorganic particulate (F) is 70 parts by weight to 200 parts by weight.If using inorganic particulate (F) When, it can further improve the refractive index of photosensitive polymer combination, therefore the refractive index for being formed by film product increases.
Additive (G)
Photosensitive polymer combination according to the present invention can further include additive (G) according to required physical property and the property changed, Being selected as in the technical field of the invention of this additive has usual skill can decision maker.In concrete example of the invention, The additive is high-molecular compound, the ultraviolet absorbing agent, anti-agglutinant, interface other than filler, alkali soluble resin (A) Activating agent saves stabilization agent, heat resistance promotor.
In preferably concrete example of the invention, the filler are as follows: glass, aluminium；Macromolecule other than alkali soluble resin (A) Compound is polyvinyl alcohol, polyalkylene glycol monoalkyl ether, poly- perfluoroalkyl acrylate alkyl ester.
Ultraviolet absorbing agent is 2- (3- tert-butyl -5- methyl -2- hydroxy phenyl) -5- chlorphenyl nitrine, alkoxy benzophenone； And anti-agglutinant is Sodium Polyacrylate.
The interfacial agent can promote the coating of composition according to the present invention, in concrete example of the invention, the boundary Fluorine-containing interfacial agent or organosilicon interfacial agent can be used in face activating agent.
In the fluorine-containing interfacial agent, end, main chain and side chain include at least a fluoroalkyl or a fluorine alkenyl.Yu Benfa In bright concrete example, which is 1,1,2,2- tetrafluoro octyl (1,1,2,2- tetra- fluoropropyl) ether, 1,1,2,2- Tetrafluoro octyl hexyl ether, eight ethylene glycol two (1,1,2,2- tetrafluoro butyl) ethers, six ethylene glycol (1,1,2,2,3,3- hexafluoro amyl) Ether, eight propylene glycol two (1,1,2,2- tetrafluoro butyl) ethers, six propylene glycol (1,1,2,2,3,3- hexafluoro amyl) ether, perfluor dodecane Base sodium sulphate, ten fluorine dodecane of 1,1,2,2,8,8,9,9,10,10-, 1,1,2,2,3,3- hexafluoro decane, fluothane benzene sulfonic acid sodium salt, Fluothane sodium phosphate, fluothane carboxylic acid sodium, fluothane polyoxyethylene ether, two glycerine four (fluothane polyoxyethylene ether), fluothane ammonium iodine, fluothane Glycine betaine, fluothane polyoxyethylene ether, perfluor alkane polyoxyethylene ether, perfluoroalkyl alkanol.It, should in another concrete example of the invention Fluorine-containing interfacial agent be BM-1000, BM-1100 (BM CHEMIE system), Megafac F142D, F172, F173, F183, F178, F191, F471, F476 (big Japan's ink and chemical industry system), Fluorad FC170C, FC-171, FC-430, FC- 431 (Sumitomo Chemical systems), Chlorofluorocarbons S-112, S-113, S-131, S-141, S-145, S-382, SC-101, SC-102, SC- 103, SC-104, SC-105, SC-106 (Asahi Glass system), F Top EF301,303,352 (new autumn fields chemical conversion system), Ftergent FT-100、FT-110、FT-140A、FT-150、FT-250、FT-251、FTX-251、FTX-218、FT-300、FT-310、FT- 400S (NEOSU system).
Organosilicon interfacial agent be TORE organosilicon DC3PA, DC7PA, SH11PA, SH21PA, SH28PA, SH29PA, SH30PA、SH-190、SH-193、SZ-6032、SF-8427、SF-8428、DC-57、DC-190(Dow Corning Toray Silicone system), (GE Toshiba is organic by TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4452 Silicon system).
In addition to fluorine-containing interfacial agent above-mentioned or organosilicon interfacial agent, which is polyxyethylated Ether, such as ethoxylated dodecyl alcohol, polyoxyethylene 8 stearate ether, polyoxyethylene oleyl ether；Polyoxyethylene aryl ether, such as polyoxy second Alkene n-octyl phenylate, polyoxyethylene n-nonyl phenol ether；Polyoxyethylene dialkyl ester, such as polyoxyethylene tin dilaurate, polyoxy second Alkene distearyl acid；Non-ionic surfactant, such as KP341 (SHIN-ETSU HANTOTAI's chemistry system), poly flow No.57,95 (common prosperity society greases Chemical industry system).
Foregoing interface activating agent can be used alone or as a mixture.
The preservation stabilization agent can be sulphur, quinone, quinhydrones, poly oxide, amine, nitroso compound or nitro.Its concrete example is 4- metoxyphenol, (N- nitroso-N- phenyl) azanol aluminium, 2,2- thiobis (4- methyl-6-tert-butylphenol), 2,6- bis-- Tert-butyl phenol.
The heat resistance promotor can be N- (alkoxy methyl) glycoluril compounds, N- (alkoxy methyl) melamine.N- (alkoxy methyl) glycoluril compounds concrete example is N, N, N', N'- tetra- (methoxy) glycoluril, N, N, N', tetra- (ethoxy of N'- Ylmethyl) glycoluril, N, N, N', N'- tetra- (n-propoxymethyl) glycoluril, N, N, N', N'- tetra- (i-propoxymethyl) glycoluril, N, N, N', N'- tetra- (n-butoxy methyl) glycoluril, N, N, N', N'- tetra- (t-butoxymethyl) glycoluril；Preferably N, N, N', N'- Four (methoxy) glycolurils.The concrete example of N- (alkoxy methyl) melamine is N, N, N', N', N ", (methoxyl group of N "-six Methyl) melamine, N, N, N', N', N ", N "-six (ethoxyl methyl) melamine, N, N, N', N', N ", N "-six (positive third Oxygroup methyl) melamine, N, N, N', N', N ", N "-six (i-propoxymethyl) melamine, N, N, N', N', N ", N "-six (n-butoxy methyl) melamine, N, N, N', N', N ", N "-six (t-butoxymethyl) melamine；Preferably N, N, N', N', N ", N "-six (methoxy) melamine.Commercially available product such as NIKARAKKU N-2702, MW-30M (three and chemistry system).
Additive (G) usage amount according to the present invention is to have usual skill in the technical field of the invention to determine Person, preferably, being based on alkali soluble resin (A) 100 parts by weight, the usage amount of the additive (G) is 0 parts by weight to 10 weight Part, preferably 0 parts by weight to 6 parts by weight, so to be more preferably for 0 parts by weight to 3 parts by weight.
Prepare film and the element with film
The present invention provides the film on a kind of substrate, is coated on substrate by photosensitive polymer combination above-mentioned, Again through pre-baked processing, exposure-processed, development treatment and after bake processing processing obtained by.
Preferably, the film be the planarization film of TFT substrate in liquid crystal display element or organic electro-luminescent display, The protective film of the core material or cladding material of interlayer dielectric or optical waveguide.
The coating method of film is not particularly limited according to the present invention, can be by spray coating method, rolling method, method of spin coating The coating methods such as (spin-coating method), slit die coating process, stick coating method, ink-jet method preferably use spin-coating method or slit die coating process, will The photosensitive polymer combination is coated on substrate, then is removed solvent through pre-baked (prebake) mode and formed pre-baked film. Wherein, pre-baked condition, different according to the type of each component, compounding ratio, usually temperature carries out between 60 DEG C to 110 DEG C 30 seconds to 15 minutes.Preferably, the film with a thickness of 3 μm to 6 μm.
After pre-baked, which is exposed under mask, expose used in light can be such as, but not limited to ultraviolet light, Far ultraviolet, X-ray, charged particle beam；Ultraviolet light can be such as g line (wavelength 436nm), h line, i line (wavelength 365nm), far Ultraviolet light can be such as KrF excimer laser, and X-ray can be such as sync plus white radioactive ray, and charged particle beam can such as electronics Beam etc..Preferably ultraviolet light is more preferably g line or i line.When selecting ultraviolet light, ultraviolet lamp grain is such as but unlimited In high mercury vapor lamp, superelevation mercury vapor lamp and metal halid lamp；Preferably, light exposure is 50 to 1500J/m2。
Development is impregnated in a developer solution, different according to the composition of composition, lasts 30 seconds to 2 minutes, with removal Should not part and form specific pattern.The concrete example of the developer solution are as follows: (1) inorganic base, as sodium hydroxide, potassium hydroxide, Sodium carbonate, sodium metasilicate, metasilicic acid acid sodium and ammonia；(2) first order fatty amine, such as ethamine, n-propylamine；(3) second level fatty amine, Such as diethylamine, n-propylamine；(4) third level fatty amine, such as trimethylamine, diethylmethyl amine, dimethylethyl amine and triethylamine； (5) third level fat naphthenic acid, such as pyrroles, piperidines, N- methyl piperidine, N- methyl 1,11 carbon of 8- diazabicyclo [5.4.0] -7- Alkene and 1,5- diazabicyclo [4.3.0] -5- nonene；(6) third level aromatic amine, such as pyridine, methylpyrimidine, lutidines, And quinoline；And (7) fourth stage ammonium salt alkali compounds, such as tetramethylammonium hydroxide, the aqueous solution of tetraethyl ammonium hydroxide.
In addition, water-miscible organic solvent and/or surfactant also can optionally make an addition to above-mentioned aobvious such as methanol, ethyl alcohol In shadow liquid.In addition, developing method can be such as, but not limited to the sides appropriate such as fluid containing method, infusion process, concussion infusion process, douche Method.
When the developer solution constituted using above-mentioned alkali compounds, cleaned usually after development with water, then with compressed air Or compressed nitrogen air-dries.Also, a post-exposure processing is also preferably carried out using high-pressure sodium lamp etc., which is irradiated comprehensively and is put Ray.More preferably, the light exposure in post-exposure step is 2000 to 5000J/m2。
Then, (postbake) is baked after carrying out using devices such as heating plate or baking ovens to handle, and makes the curing of coating.Temperature is baked afterwards Degree is usually 120 to 250 DEG C.Wherein, the roasting time is type according to heating machine and different and adjust afterwards, for example, using adding The heating time of hot plate is 5 to 30 minutes, and the heating time using baking oven is 30 to 90 minutes.Processing step more than Afterwards, a film can be formed.
The substrate can be selected from using alkali-free glass, soda-lime glass, strengthened glass (Pyrex glass in a liquid crystal display Glass), adhered to the substrate of glass of transparent conductive film etc. and the photoelectricity for solid photographic element etc. on quartz glass or surface Inverting element substrate (such as: silicon substrate).
The present invention provides a kind of element again, and it includes films above-mentioned.
Element according to the present invention is including but not limited to display element, semiconductor element or optical waveguide etc..
Photosensitive polymer combination of the invention be formed by film with good refractive index and with molybdenum adherence.
The present invention is hereby described in detail with the following example, does not mean that present invention is limited only by these embodiment institutes only The content of announcement.
Specific embodiment
Prepare alkali soluble resin (A)
Synthesis example 1
By fluorenes ring oxygen compound (model ESF-300, the Nippon Steel's chemistry system of 100 parts by weight；Epoxide equivalent 231), 30 weights Measure the acrylic acid of part, the benzyltriethylammonium chloride of 0.3 parts by weight, 0.1 parts by weight 2,6-di-tert-butyl p-cresol and 130 The propylene glycol methyl ether acetate of parts by weight is added with continous way addition manner into the four-hole boiling flask of 500mL, and pan feeding speed control For system in 25 parts by weight/minute, the temperature of the reaction process maintains 100 DEG C~110 DEG C, reacts 15 hours, it is solid to can be obtained one Constituent concentration is the pale yellow transparent mixed liquor of 50wt%.
Then, the above-mentioned resulting pale yellow transparent mixed liquor of 100 parts by weight is dissolved in the ethylene glycol ethyl ether of 25 parts by weight In acetate, and the tetrabydrophthalic anhydride of 6 parts by weight and the benzophenone tetracarboxylic dianhydride of 13 parts by weight are added simultaneously, and Be heated to 110 DEG C~115 DEG C, react 2 hours, can obtain an acid value be 98.0mgKOH/g with unsaturated group resin (with It is referred to as A-1-1 down).
Synthesis example 2
By fluorenes ring oxygen compound (model ESF-300, the Nippon Steel's chemistry system of 100 parts by weight；Epoxide equivalent 231), 30 weights Measure the acrylic acid of part, the benzyltriethylammonium chloride of 0.3 parts by weight, 0.1 parts by weight 2,6-di-tert-butyl p-cresol and 130 The propylene glycol methyl ether acetate of parts by weight is added in the four-hole boiling flask for setting 500mL with continous way addition manner, and pan feeding speed control For system in 25 parts by weight/minute, the temperature which crosses maintains 100 DEG C~110 DEG C, reacts 15 hours, it is solid to can be obtained one Constituent concentration is the pale yellow transparent mixed liquor of 50wt%.
Then, the above-mentioned resulting pale yellow transparent mixed liquor of 100 parts by weight is dissolved in the ethylene glycol ethyl ether of 25 parts by weight In acetate, and the benzophenone tetracarboxylic dianhydride of 13 parts by weight is added, 2 hours, then, addition are reacted at 90 DEG C~95 DEG C The tetrabydrophthalic anhydride of 6 parts by weight, and reacted 4 hours at 90 DEG C~95 DEG C, can obtain an acid value is 99.0mgKOH/g The resin (hereinafter referred to as A-1-2) with unsaturated group.
Synthesis example 3
By epoxide [model NC-3000, Japanese chemical drug (strain) system of 400 parts by weight；Epoxide equivalent 288], 102 weights Measure the acrylic acid of part, the methoxyl group phenol (methoxyphenol) of 0.3 parts by weight, 5 parts by weight triphenylphosphine and 264 parts by weight Propylene glycol methyl ether acetate be placed in a reaction flask, the temperature which crosses maintains 95 DEG C, reacts 9 hours, can be obtained One acid value is the intermediate product of 2.2mgKOH/g.Then, the tetrabydrophthalic anhydride of 151 parts by weight is added (tetrahydrophthalic anhydride) reacts 4 hours at 95 DEG C, and can obtain an acid value is 102mgKOH/g, and The resin (hereinafter referred to as A-1-3) with unsaturated group that weight average molecular weight is 3,200.
Synthesis example 4
Nitrogen inlet, blender, heater, condenser pipe and temperature are set on 1000 milliliters of a volume of four cervical vertebra bottles Meter after importing nitrogen, adds the methacrylic acid of 30 parts by weight, the glycidyl methacrylate of 35 parts by weight, 10 parts by weight 1,3- butadiene, the styrene of 25 parts by weight, the 2,2'- azo two (2- methylbutyronitrile) of 2.4 parts by weight and 240 parts by weight Diethylene glycol dimethyl ether solvent.Then, being slowly stirred above-mentioned composition makes solution be warming up to 85 DEG C, and polycondensation at a temperature of this 5 hours.Then, by after solvent devolatilization, an alkali soluble resin (A-2-1) can be obtained.
Synthesis example 5
Nitrogen inlet, blender, heater, condenser pipe and temperature are set on 1000 milliliters of a volume of four cervical vertebra bottles Meter after importing nitrogen, adds the 2- methacryloyloxyethyl succinate of 10 parts by weight, the methacrylic acid 3 of 50 parts by weight, 4- epoxycyclohexanecarboxylate, the 2-hydroxyethyl methacrylate of 20 parts by weight, 10 parts by weight the bicyclic pentyl ester of methacrylic acid, The styrene of 10 parts by weight, the 2,2'- azo two (2- methylbutyronitrile) of 2.4 parts by weight and the diethylene glycol two of 240 parts by weight Methyl ether solvent.Then, being slowly stirred above-mentioned composition makes solution be warming up to 85 DEG C, and polycondensation 5 hours at a temperature of this.Then, After solvent devolatilization, an alkali soluble resin (A-2-2) can be obtained.
Synthesis example 6
Nitrogen inlet, blender, heater, condenser pipe and temperature are set on 1000 milliliters of a volume of four cervical vertebra bottles Meter after importing nitrogen, adds the acrylic acid of 15 parts by weight, the glycidyl methacrylate of 30 parts by weight, the first of 20 parts by weight Base acrylic acid 2- hydroxy methacrylate, the benzyl methacrylate of 35 parts by weight, 2.4 parts by weight (the 2- methyl fourth of 2,2'- azo two Nitrile) and 240 parts by weight diethylene glycol dimethyl ether solvent.Then, being slowly stirred above-mentioned composition makes solution be warming up to 85 DEG C, and Polycondensation 5 hours at a temperature of this.Then, by after solvent devolatilization, an alkali soluble resin (A-2-3) can be obtained.
Prepare photosensitive polymer combination
Embodiment 1
By the alkali soluble resin (A-1-1) of 100 parts by weight, p- cumylphenyl (methyl) acrylic acid of 15 parts by weight 1- [9- ethyl -6- (2- methyl benzoyl group) -9H- carbazole -3- substituent group]-ethane ketone -1- (O- of ester (B-1-1), 10 parts by weight Acetyl group oxime) (C-1), 3 parts by weight bis- (2- diphenylphosphinoethyl)-methylsilyl ethyl triethoxysilanes (E-1-1) With titanium dioxide (the average grain diameter 13.14nm of 50 parts by weight；F-1 the propylene glycol methyl ether acetate (D-1) of 500 parts by weight) is added In, after mixing evenly with swing-out stirrer, it can be prepared by the photosensitive polymer combination of embodiment 1.
Embodiment 2 to 11 and comparative example 1 to 3
Embodiment 2 to 11 and comparative example 1 to 3 are using identical as the photosensitive polymer combination production method of embodiment 1 Operating method, the difference is that embodiment 2 to 11 and comparative example 1 to 3 be change photosensitive polymer combination in raw material Type and its usage amount, particulars and subsequent evaluation result are loaded in table 1 respectively.Evaluation method
1. refractive index
By above-mentioned photosensitive polymer combination in being obtained in a manner of rotary coating on element glass substrate (100x100x0.7mm) About 2 μm of film connects and with 90 DEG C after pre-baked 2 minutes, mask is placed between exposure machine and film, is then 100mJ/ with energy cm2Ultraviolet light film, the film after exposure is impregnated in KOH aqueous solution 50 seconds of the 0.045% of 23 DEG C, removing do not expose The part of light.After finally cleaning with clear water, then to bake 30 minutes after 235 DEG C, it can get a film.
Then, in 25 DEG C of thermostatic chamber, laser and PC-2010 prism-coupled instrument (the Metricon public affairs of 633nm are used Department system) measure the refractive index of above-mentioned film.
Shuai≤1.65 She ◎: Zhe；
Zero: 1.65 Shuai≤1.60 > Zhe She；
△: 1.60 Shuai≤1.55 > Zhe She；And
X: refractive index < 1.55.
2. molybdenum adherence
By above-mentioned photosensitive polymer combination on the element glass substrate (100x100x0.7mm) for be coated with molybdenum with rotation Coating method obtains about 2 μm of film, connects and after pre-baked 2 minutes, mask is placed between exposure machine and film with 90 DEG C, then with Energy is 100mJ/cm2Ultraviolet light film, the film after exposure is impregnated in the KOH aqueous solution of the 0.045% of 23 DEG C 50 seconds, remove unexposed part.After finally cleaning with clear water, then to bake 30 minutes after 235 DEG C, it can get a film.Later, According to netted lattice (cross-hatched) measuring method of the 8.5.2 in (1900) 8.5 adherence test method(s) of JIS.K5400 come It is evaluated, above-mentioned film is cut into 100 netted lattice with pocket knife, then to tear after adhesive tape adhesion, it is remaining to observe netted lattice Situation, the netted lattice quantity to fall off is fewer, and it is better with the adherence of molybdenum plated film to indicate.According to assessment level shown below, and Adherence is evaluated using four grades:
◎: no any netted lattice fall off；
Netted lattice Shuo Liang≤5% that zero: 0% < falls off；
Netted lattice Shuo Liang≤35% that △: 5% < falls off；And
Netted lattice Shuo Liang≤100% that X:35% < falls off.
According to the embodiment of upper table 1 and comparative example evaluation result it is found that when photosensitive polymer combination uses silane chemical combination When object (E-1), be formed by film with good refractive index and with molybdenum adherence.In addition, working as photoresist group When closing object and containing resin (A-1) with unsaturated group, compound (B-I) and/or inorganic particulate (F), it is formed by film Refractive index is preferable, and when photosensitive polymer combination contains compound (B-1), be formed by film and molybdenum adherence compared with It is good.When photosensitive polymer combination does not use silane compound (E-1), it is formed by the refractive index and and molybdenum of film Adherence is bad.
Although the present invention is disclosed above with embodiment, however, it is not to limit the invention, the skill belonging to the present invention Any tool usually intellectual in art field, without departing from the spirit and scope of the present invention, when various change and profit can be made Decorations, therefore protection scope of the present invention is subject to the range defined depending on appended claims.
Figure BDA0001070387350000351

Claims (8)

1. a kind of photosensitive polymer combination, characterized by comprising:
Alkali soluble resin (A), including the resin (A-1) with unsaturated group, the wherein resin (A-1) with unsaturated group It is to be reacted by a mixture and obtained, and the mixture includes epoxide (a-1-1) and tool at least two epoxy groups There are at least one carboxylic acid group and the compound (a-1-2) of at least one ethylene unsaturated group, in which:
It includes tying shown in formula (a-I) and/or formula (a-II) that this, which has the epoxide (a-1-1) of at least two epoxy groups, Structure:
Figure FDA0002131551840000011
In formula (a-I), R1、R2、R3And R4It is respectively independent to indicate hydrogen atom, halogen atom, the alkyl that carbon number is 1 to 5, carbon number For 1 to 5 alkoxy, carbon number be 6 to 12 aromatic radical or carbon number be 6 to 12 aralkyl；
In formula (a-II), R5To R18The alkyl or carbon number that respectively independent expression hydrogen atom, halogen atom, carbon number are 1 to 8 are 6 To 15 aromatic radical；And the n indicates integer of 0 to 10；
Compound (B) with ethylene unsaturated group；
Light initiator (C)；
Solvent (D)；And
Silane compound (E), wherein the silane compound (E) includes the silane compound (E-1) as shown in formula (I):
Figure FDA0002131551840000021
In formula (I), A respectively stands alone as singly-bound, alkylidene or secondary aryl, and B respectively stands alone as the organic group of tool diphenylphosphino Group, hydrogen atom, alkyl, aryl or-OR, wherein R is the alkyl or phenyl that carbon number is 1 to 6,
Wherein, at least one B is the organic group for having diphenylphosphino, at least one B is-OR, and when B is-OR, is connected with B The A connect is singly-bound.
2. photosensitive polymer combination as described in claim 1, wherein the usage amount based on the alkali soluble resin (A) is 100 parts by weight, it is 15 parts by weight to 300 parts by weight, the light initiator (C) that this, which has the compound (B) of ethylene unsaturated group, Usage amount be 10 parts by weight to 100 parts by weight, the usage amount of the solvent (D) is 500 parts by weight to 3000 parts by weight, the silane The usage amount of compound (E) is 1 parts by weight to 12 parts by weight, and the usage amount of the silane compound (E-1) is 1 parts by weight to 10 weights Measure part.
3. photosensitive polymer combination as described in claim 1, wherein there is the compound (B) of ethylene unsaturated group to wrap for this Include following formula (b-I) and/or formula (b-II) compound represented (B-1):
In formula (b-I), R21And R22Hydrogen atom or methyl are respectively independently represented, p indicates 0 to 4 number；
Figure FDA0002131551840000023
In formula (b-II), R23And R24Hydrogen atom or methyl are respectively independently represented, m indicates 0 to 4 number.
4. photosensitive polymer combination as claimed in claim 3, wherein the usage amount based on the alkali soluble resin (A) is 100 parts by weight, the usage amount of the compound (B-1) are 15 parts by weight to 100 parts by weight.
5. photosensitive polymer combination as described in claim 1, it is characterised in that further include inorganic particulate (F), wherein the nothing The material of machine particle (F) includes the oxide of tetrels.
6. photosensitive polymer combination as claimed in claim 5, wherein the usage amount based on the alkali soluble resin (A) is 100 parts by weight, the usage amount of the inorganic particulate (F) are 50 parts by weight to 250 parts by weight.
7. a kind of film, it is characterised in that it is to be coated with photosensitive polymer combination described in any one of claims 1 to 6 In on a substrate, then through pre-baked processing, exposure-processed, development treatment and after bake obtained by processing processing.
8. a kind of element, it is characterised in that include film as claimed in claim 7.
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